Potentially reactive curable polymers



Patented July 24, 1951 POTENTIALLY REACTIVE CURABLE POLYMERS Emil E. Novotny, Prospectvillc, George Karl Vogelsang, La Mott, and Ernestll. Novotny, Philadelphia, Pa... assignors, by mesne assignments, to The BordenCoinpany, New York, N. Y., a corporation of New Jersey No Drawing. Application November 21, 1944', Serial No. 564,554

16 Claims.

The present invention relates to potentially reactive compositions which possess the faculty of being partially or completely convertible to the infusible, infusible thermo-rigid, or vulcanized rubbery state. the present invention is drawn to potentially reactive curable compositions which are made by mixing a compound selected from the class comprising the saturated halogenation products of the aldehydes of the mono hetero atomic five. 'membered rings and their reactive derivatives,

with a polymeric organic compound containing a plurality of atomic groups reactive with compounds selected, from the clas comprising the saturated halogenation products of the aldehydes,

oi the mono hetero atomic five membered rings and their reactive derivatives, said reactive atomic groups being present in the proportion of at least one such group per thousand atoms of the aforesaid polymeric organic compound.

The prime object of the present invention is the production of potentially reactive curable compositions that can be converted to an infusi ble, infusible thermo-rigid, or vulcanized rubbery state.

A further object is to provide means whereby nominally thermoplastic compositions can be converted into potentially reactive curable compositions which, when cured, are possessed of a higher than usual degree of heat insensitiveness.

More specifically stated,.

A further object is to provide means whereby nominally thermoplastic compositions can be converted into potentially reactive curable compositions which, when cured, are possessed of a higher than usual degree of solvent resistance. A further object is the production of a new class of potentially reactive curable compositions that is preeminently adapted for the manufacture of resinous, plastic, and rubbery compositions suitable for use in press, injection, extru-- A further object is the production of potentially reactive compositions that can be cured to yield rubbery vulcanizates of superior and outstanding properties.

. In it essence the potentially reactive curable,

a co-agent.

2 compositions of the present invention are prepared by mixing together a curing agent with The curing agent is essentially a compound selected from the class comprising the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings and their reactive derivatives. These curing agents are unusuall reactive compounds, reacting as they do, with an exceedingly wide variety of functionally reactive atomic groups. The presence of such reactive atomic groups in a polymeric organic compound inexorably imparts to the compound the faculty of being able to enter into a curing reaction with the aforedescribed class of curing agents. A wide variety of naturally occurring polymeric organic compounds contain the requisite reactive atomic groups and, as such, are suitable for use in the present invention. An almost endless variety of polymeric organic compounds may be synthesized so as to contain the requisite reactive atomic groups so as to suit them for use as co-agents.

Through the teachings of the present invention it becomes possible to advantageously prepare a virtually limitless number of potentially reactive curable compositions without recourse to any of the usual curing or vulcanizing agents. Unique and distinctive curable compositions may be made from a wide variety of polymeric compounds which are ordinarily regarded as non-curable by rendering such compounds susceptible to cure after the manner disclosed in copending application (Serial No. 495,036 filed July 16, 1943 and now abandoned), and as also indicated further on in the present specifications, and then admixing the same with a material selected from the class consisting of the saturated halogenation products of the aldehydes'oi the mono hetero atomic five membered rings and their reactive derivatives as curing agent. i

In brief the present invention discloses means whereby the majority of the known curable polymeric' materials can b cured via the helogenation products of the aldehydes of the mono hetero atomic five membered rings and their reactive derivatives as curing'agents and also discloses how curable compositions can be made out of polymeric materials that have heretofore been .and cooling facilities.

tive derivatives a curing agents and upon the use of polymers which contain certain essential potentially reactive atomic groups, it is desirable in the interest of clarity to define these interreactable components. I

The saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings may be produced by the methods described in copending application, Serial No. 464,524, filed November 4, 1942, now Patent No. 2,490,462, patented December 6,1949. The reactive derivatives of the said halogenated aldehydes are in part described in the afore-alluded to application'but are more fully described in copending application, Serial No. 466,480, filed November 21, 1942, now Patent No. 2,475,801, patented July 12, 1949. For the sake of completeness, we give below a brief description of the synthesis of these unique curing agents.

The saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings may be produced through the method which comprises thesteps of diluting a mole of one or more of the said aldehydes with at leasta mole of solvent and then'rapidly introduce halogen in the proportion of substantially four atoms of halogen-per molecule of the said aldehyde while -mainta-ining the temperature below the point of 1 said dehalogenation to involve an average removal of less than of the original halide content of the halogenated aldehydes.

From the standpoint of ease of production and general reactivity the fully saturated chlorination product of furiural is perhaps of the greatest interest in connection with the present invention although we wish to emphasize that all of the saturated halogenation products of the aldehydes of themono hetero atomic five membered rings and theirv reactive derivatives, are useful. for the purpose f.curing up the products of the present invention. The following is an illustrative. ex-

ample of the manner in which the saturated chlorination product of furfuralmay be produced. Fifteen parts of dry, pure furfural are dissolved infifty parts of carbon tetrachloride in a glasslinedchl'orinator provided with a suitable stirrer Chlorine is passed into themixture at as rapid a rate as it consistent with the, cooling facilities and the attainment of a good absorption eificiency. The solution should be. permitted to absorb approximately 22.2 parts of chlorine. The temperature is best kept from rising above 100 F. and is preferably kept below 80 F. The resultant solution of fully chlorinated furfural is very stable and such a solution, on standing for a period of a year, shows no appreciable change. Such mixtures. may also be refluxed for considerable periods of time. without undergoing any discernible change. The mixture may be concentrated under vacuum. so. as to remove the diluentv Towardsthe end of. this operation the vacuum may advantageously .be increased and the temperature may be raised, to in the neighborhood of 125 C. to assure a thorough removal of the volatiles.

More specific details for the-carrying out of the. above process as well as the halogenation of heterocyclic aldehydes other than furfural' and 4 procured from the copending application, Serial No. 464,524, now Patent No. 2,490,462, already referred to.

The reactive derivatives of the-saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings are of particular interest in connection with the present invention and may be produced by subjecting the said halogenated aldehydes to the action of heat either per se or in the presence of any one of innumerable reagents. When the aforesaid halogenated aldehydes are subjected to the action of heat either per se or in the presence of substantiallyinert solvents, there may be produced derivatives which are chemically even more reactive than the progenitors themselves. When the saturated aldehydes are reacted with other reactants an almost unlimited variety of products may be produced. Such reaction products function as curing agents provided that they contain more than 25% of the original halogen atoms contained in the halogenated aldehyde. The reactive derivatives of the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings may be referred to as the prodnets of partial dehalogenation. It appears tobe immaterial as to how the partial de-halogenati'on is achievedseemingly all the reaction products, provided that they retain at least 25% of the original halogen content, function as curing agents.

Representative of suitable co-reagents iorthe production of reactive derivatives out of the saturated halogenation products of the aldehydes of .the mono hetero atomic five membered" rings are: water; ammonia and all manner or ammonia derivatives; alkali metals, oxides and hydroxides; alkaline earth metals, oxides and hydroxides; heavy metals, as well as their oxides and hydroxides in the active state; carbonates, sulphides, sulphites, borates, the salts of weak inorganic acids, as well as the salts of virtually all organic acids; and organic compounds of all sorts, virtually without qualification.

In producing the reactive derivatives'the only requisite is that the reaction conditions as regards pressure, temperature,. time, etc:, as well as the chemical co-reagents, if any,be such that the de-halogenation shall not be carried beyond the point where more than '75 percent ofthe halogenated aldehydes original halogen content isremoved. When more than three-quarters of the. original halogen content is removed in'the process of de-halogenation,. then the resultant reaction products may be characterized as falling outside of the scope of reactivity where they satisfactorily function as curing'agents.

Of the known aldehydesfof the. mono hetero atomic five membered rings furfural is by far the most abundant and, indeed, because of its agricultural origin, may be said to be inexhaustible. For this reason the present inventors, in themajority'of the ensuing illustrativeexamples;.1istas the preferred curing agent the saturated'ho'lagenation product of furfural and the reactive derivatives thereof. It should be clearly understood, however, that the saturated halogenation-products of the aldehydes of the monohetero atomic five membered rings other than furfural are usable.

Chlorine is.by far the most abundant,..most available, andv most widely distributed halogen element in the earths crust. For this reason, in most of the ensuing examples, the presentinventors have, for purposes of illustration, listed a period of five hours. *tially distilled, first under a pressure of from 100 the saturated chlorination product of furfural and the reactive derivatives thereof asthe preferred curing agents. It is to be distinctly understood, however, that the halogenation products of thehalogens other than chlorine, that is fluorine, bromine, and iodine, are also usable in thempresent invention as are also the mixed .halogenation products.

ingis completed in approximately two to three hours,and1 the final weight of residuum should be between 41 and 42 parts. The. above product is ecidedly more fluid than the original chlorinatedsiurfural and is possessed of a chlorine content of. 55.07 per cent.

A mixturecomprising 47.6 parts of chlorinated turfural and 47.6 parts of xylene is refluxed for The mixture is then parto 300 mm. of Hg, and then under a pressure of less than mm. of Hg. The temperature may advantageously be kept at 325 F. and the heat is maintained until the rate of distillation appreciably slows up and the weight of residuum falls within the range of approximately to 38 parts.

This de-halogenated reactive derivative contained 53.5 per cent of chlorine, possessed an acid number of 126, a saponification number of 173, a mean molecular weight of approximately 450,

and a specific gravity of 1.619.

A mixture comprising 52.5 parts of chlorinated furfural and 96.0 parts of methanol is refluxed for a period of' about ten hours when a loss in weight of approximately 18.0 parts will occur.

The loss in weight is almost exclusively due to evolved methyl chloride. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg.

and methoxy group content 21.45 per cent.

' A mixture comprising 47.56 parts of chlorinated furfural and 8.02 parts of methanol is refluxed until an initial loss in weight of approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under a pressure of from 100 to .300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield approximately 41.8 parts of a partially dehalogenated reactive derivative containing 43.0 per cent of chlorine and 12.06 percent of methoxy. A mixture comprising 47.56 parts of chlorinated furfural; 64.08 parts of methanol, and 1.8 parts of water is refluxed until an initial loss in weight of' approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under 2, pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of' Hg to yield 41.6 parts of a partially de-halogenated reactive derivative containing 37.07 per cent of chlorine and 16.01 per cent of methoxy.

Calcium carbonate, 5.0 parts, is slowly added to a solution comprising 47.6 parts of chlorinated furfural'dissolved in 70.0 parts of methanol. The

mixture is then heated and kept hot for a short periodof time andis then concentratedundera pressure of from to 300 mm. of Hg to a weight of approximately 70.5 parts. The further processing. is optional, but the following gives good results: To the concentrate add. 60.0 parts of benzene, and 32.0 parts of water. Shake, separate the layers, dry the benzene layer, filter and, if desired, clarify with decolorizing. carbon. The benzene solution is then subjected to partial distillation, first under a pressure of from: 100 to 300 mm. of Hg and then under a pressureof less than 20mm. of Hg to yield approximately 40.9. parts of an amber colored partially. de-halogenated reactive derivative containing. 40.47 per cent of chlorine and 16.44 per cent of .methoxy.

Zinc dust, 3.27 parts, was slowly added to amix- .ture consisting of 47.6 parts of chlorinated furfural and 32.08 parts of methanol. Themixture was cooled down to prevent excessive loss through volatization. The mixture was subjected .to. partial distillation under a pressure of from 100.110 300 mm. of Hg and finally under a pressureof less than 20 mm. of Hg to yield 31.1 parts of a partially de-halogenated reactive derivative which contained 24.5 per cent of chlorine and 4.28per cent of methoxy. The aboveweight and, percentage data includes the zinc chloride synthetically formed.

Zinc chloride, 0.68 part, was added. to a mixture consisting of 47.6 parts of chlorinated furfural and 16.04 parts of methanol. The mixture was subjected to partial distillation, first under a pressure of between 100. and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hgto yield 308 parts of a partially de-halogenatedreactive derivative which contained 30.4 per centof chlorine and 7.86 per cent of methoxy. The product of this reaction was a grindably hard mass.

A solution comprising 4.1 parts of anhydrous sodium acetate dissolved in 32.08 parts of methanol was added to 47.6 parts of chlorinated furiural. The mixture was then subjected to par.- tial distillation, first under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 45.7 parts of a residuum which contained some NaCl. Sixty parts of benzene and 36.0 parts of water were added to the above residuum and after agitation, the stratified layers were separated. The benzene layer was then dried, de-colorized, and filteredand the benzene was then distilled off under reduced pressure to yield 39.0 parts of a partially tie-halogenated reactive derivative which contained 44.6 per cent of chlorine and 8.66 per cent of methoxy besides some acetal groups.

A solution comprising 11.2 parts of potassium hydroxide dissolved in 60.0 parts of methanol was slowly added to a mixture consisting of 47 .6 parts of chlorinated furfural dissolved in 20.0 parts of methanol. The mixture was subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg. Sixty parts of benzene and 36.0 parts of water were then added to the residuum and the resultant mixture after shaking, was permitted to stratify and the benzene layer was removed, dried, de-colorized, and finally freed from the benzene by vacuum concentration. Approximately 36.0 parts of a partially de-chlorinated reactive derivative were procured.

Chlorinated furfural, 14.3 parts, was dissolved in 49.0 parts of'normalb-utanol and the resultant.

.mixture was thensubjected to slow distillation,

first under a pressure of between 100 and 300 mm. of Hg and finally under a pressure of less than 20mm. of Hg to yield 12.4 parts of a reactive derivative which analyzed 51.0 per cent carbon, 7.07 per cent hydrogen, 16.1 per cent chlorine, and 25.85 per cent oxygen.

- .A mixture comprising 10.9 parts of chlorinated furfural, and 46.0. parts of. iso-butanol was sublJ'ected, first to slow fractional distillation. at atmospheric pressure and then to partial distillation. first under a pressure of 100110 300 mm.'of

Hg and finally under a pressureof less than 20 mm. of Hg to yield 11.16 parts of a. reactive derivativewhich analyzed .carbon 55.45 per cent,

hydrogen 7.62 per cent and chlorine 13.91

cent.

.: A mixture comprising 14.07 parts of chlorinated per.

furfural and 59.25 parts of .a secondary butyl alcohol was subjected first to slow fractional distillationat atmospheric pressure and then to direct partial distillation, first undera pressure of between 100 and 300 mm. of Hg and finally under .a pressure of less than 20 mm. of .Hg to yield 11.11 .parts .of .a reactive derivative which analyzed was subjected to slow fractional distillation at atmospheric pressure.v Very considerable .quantities of gas were evolved. The mixture was then subjected to direct distillation at atmospheric pressure and finally under a pressure of less than than 20 mm. of Hg to obtain 9.09 parts of derivative. Tertiary alcohols of all'sorts are more or less completely decomposed by the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings.

A mixture comprising 47 .6 parts of chlorinated furfural and 27.6:parts oi secondaryamyl alcohol withoutany'preliminary refluxing is immediately subjected to partial distillation, first under. a pressure of between 100 and 300 mm. of Hg'an'd then under a pressure :of less than 20 mm. Of. Hg to yield-41.27 parts of a partially tie-halogenated reactive derivative which contained 40.65 per cent ",Of chlorine.

A mixture comprising 47.6 parts of chlorinated furfural and 38.03 parts of the mono methyl ether of ethylene glycol was directly subjected to partial distillation under a pressure of less than 20 mm. of Hg to yield 43.52 parts of a partially de-halogenated reactive derivative which contained 37.22 per cent of chlorine and had an ,alkoxy content equivalent to 7.48 per cent calculated as methoxy.

Amixture comprising 47.6 parts of chlorinated furfural and 58.05 parts of butyl acetate was first refluxed four hours and then subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield 44.2 parts of a reactive derivative which contained 47.8.per cent of chlorine.

A mixture comprising 47.6 parts of chlorinated furfural and 31.02 parts of ethylene glycol was directly subjected to partial distillation under a pressure of less than 20 mm. of Hg to yield 44.1 parts of a partially (ls-halogenated derivative which contained 31.33 per cent of chlorine.

A mixture comprising 47.6 parts of chlorinated furfural and 40.0 parts of ethylene chlorhydrinis directly subjected to partial distillation under a pressure of less than 20 mm. of Hg to yield 44.4

parts'of'a reactive derivative which contained 50.05 per cent of chlorine. l

A mixture comprising 47.6 parts of chlorinated furfural and 29.0 parts of acetone (dimethyl ketone) was refluxed four hours and then subjected to partial distillation, first .underaipressure of from -to 300 mm. of Hg andfinally under a pressure of less than 20 mm. ofHgLto yield 41.3 parts of a reactive derivative containing 51.2 percent of chlorine.

A mixture comprising 47.6 parts of chlorinated furfural .and,36.05 parts of ethyl methyl .ketone was refluxed for two hours and then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and then under a pressure of, less than 20 mm. of Hg to yield 41.0 parts of a partially de-chlorinated reactive derivative con- ;taining 51.9 per cent. of chlorine. A mixture comprising 47.6 parts of chlorinated furfural and 56.06 parts of. di-isobutylene :was first refluxed for a period of four hours and then subjected to, partial distillation, .firstuunder a pressure oi-froin 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield 39.7 partsof a reactive derivative containing 38.6 per cent of-chlorine. 1 A mixture comprising 47;6 parts of chlorinated furfural, 32.0 parts of butanol, and 0.68 part of anhydrous zinc chloride was refluxed for'four hours and then subjected to partial distillation, first under a pressure of between.l00-'and-.-300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 23.89 parts ofa grinda-bly hard reactive derivative. containing-14.91 per cent of chlorine. A mixture comprising 24.0 parts of chlorinated furfural, 36.0 parts of mono methyl. ether, of ethylene glycol and 2.0 parts of distilled water was refluxed for. eight hours andthen subjected to distillation, first. at atmospheric pressure,.then under apressure of between 100 and 300 mm.-of Hg and then under a pressure of less than20 mm. of Hg, ending up with a kettlejacket temperature of approximately 425 F. and continuingthe reaction until the product acquired a rubbery char acter. A yield of vapproximately.11.0-parts of. a blackrubbery product was procured.v The mate.- rial analyzed chlorine 5.3 per cent, hydrogen.5.6 per cent, and carbon 52.2 per cent. This particular derivative was still perspectively reactive. Had the heating and distillation been stopped earlier a more fluid and more reactive product would have been procured and vice versa, had the heating and vacuum distillation been continued beyondthe point to which it was carried,

then substantially infusible, rubbery, and hard products are obtained which test substantially non-reactive. When chlorinated furfuralor its equivalent isreacted: with the mono methyl or mono .ethyl ether of ethylene glycol a .very. large quantity of alkyl halide is generated.

A mixture comprising 2.38 parts of chlorinated furfural and 3.6 parts of butyl aldehyde is refluxed for four hours and then subjected to partial distillation first at atmospheric pressure and then under a pressure of less than 20 mm. of Hg until at a temperature of 300 F. nothing further distills oil. A yield of 3.36 parts is procured which analyzed 70.7 per cent of carbon, 8.38 per cent of hydrogen, and 7.56 per cent of chlorine. A mixture comprising 2.38 parts of chlorinated furfural, 4.64 parts of the methyl ester of alpha methoxy isobutyric acid was refluxed for three hours and then subjected to partial distillation under a pressure of less than 20 mm. of Hg at a temperature of 340 F. to yield 1.26 parts of a reactive product.

Anhydrous aluminum chloride, 2.67 parts, is cautiously added to a mixture comprising 4.2 parts of chlorinated furfural and 4.7 parts of benzene. The mixture was then refluxed upon a water bath for about two hours and then 20.0 parts of water and 8.0 parts of benzene were added along, with a little hydrochloric acid and the mixture was refluxed for thirty minutes. The mixture was then permitted to cool, the layers separated, and the benzene solution was decolorized, filtered, and then concentrated by evaporation at a temperature of 212 F. at a pressure of less than 20 mm. of Hg. A more or less reactive hard product weighing 5.67 parts was procured.

Anhydrous aluminum chloride, 2.67 parts, was added to a mixture consisting of 4.2 parts of chlorinated furfural and. 20.23 parts of di-isobutylene. After the aluminum chloride had been added the mixture was permitted to cool somewhat and 1.0 part of hydrochloric acid along with20.0 parts of water were added. The mixture was refluxed thirty minutes. After cooling the layers were separated. The organic layer was filtered and the benzene and excess di-isobutylene, etc., were distilled off, yielding 7.61 parts as the derivative.

A mixture comprising 4.5 parts of chlorinated furfural and 3.1 parts of a-terpineol was heated upon a water bath for one hour. The temperature was then raised to 300 F. under a pressure of between 100 and 300 mm. of Hg and then to 350 under the same pressure until a grindably hard product weighing 4.29 parts was procured.

A mixture comprising 4.0 parts of chlorinated furfural, 12.0 parts ofdiethylene glycol and 3.53 parts of water was refluxed for a period of several hours and then subjected to partial distillation, first under a pressure of 100 to 300 mm. of Hg and then under a pressure of less than mm. of Hg, ending up with a residuum weighing 2.59 parts.

,A mixture comprising 4.0 parts of chlorinated furfural and 8.0 parts of aqueous (40%) formaldehyde was refluxed for eight hours and then after separating the layers, the organic layer was distilled under a pressure of from 100 to 300 mm. of Hg to yield 2.56 parts of a moderately hard, solid material possessed of a fair reactivity.

A mixture comprising 4.0 parts of chlorinated furfural and 4.0 parts of cotton seed oil was heated to 200 F. for thirty minutes, then at 325 F. for two hours, and finally at 350 F. for about two hours. Considerable quantities of gaseous vproduct (HCl) were evolved. If the mixture be heated for a further period of time then the product passes over into a rubbery composition. Material of this sort by being subjected to temperature in excess of 350 F. for a period of two or more hours can be converted into a material suitable for the manufacture of friction elements and brake blocks.

A mixture comprising 8.0 parts of chlorinated furfural and 24.0 parts of water was refluxed for a period of one hour. layers, one in an aqueous phase and the other in an organic phase. The mixture was then subjected to partial distillation under a pressure of 100 to 300 mm. of Hg yielding 3.68 parts of derivative analyzing 26.45 per cent chlorine.

A solution consisting. of 4.76 parts of chlorinated furfural dissolved in 7.0 parts of meth- The material was in two anol was added to a solution comprising 6.56 parts of anhydrous sodium acetate dissolved in 35.0 parts of methanol. The mixture was then refluxed for one hour and let cooled. The product was suction-filtered, the filtrate being washed with an additional quantity of methanol. The filtrate was then subjected to partial evaporation, first at atmospheric pressure and then under a pressure of from to 300 mm. of Hg. A residuum of 9.0 parts resulted. This latter was then extracted with anhydrous ethyl acetate, filtered and reconcentrated so as to evaporate off the ethyl acetate. The residuum which comprised the main reaction product weighed 4.0 parts and had a chlorine content of approximately 10 per cent.

Anhydrous aluminum chloride, 2.67 parts, was added to a mixture comprising 4.2 parts of chlorinated furfural and 19.39 parts of mono chloro benzene. Approximately one and onehalf hours was utilized in introducing the aluminum chloride at the end of which time the mixture was kept cool for an additional thirty minutes, and thereafter, it was refluxed for a period of one hour. The mixture was then cooled to F. and 1.0 part of concentrated hydrochloric acid and 20.0 parts of. water were added. The material was refluxed for thirty minutes, the layers separated, the organic layer filtered and the latter then subjected to partial distillation under a pressure of from 100 to 300 mm. of Hg until at an end temperature of 400 F. nothing further distilled over. A yield of 8.33 parts of a highly viscous material resulted.

A mixture comprising 9.52 parts of chlorinated furfural and 1.84 parts of glycerine is heated to 212 F. for a period of two hours, then at 275 F. for a period of one hour, then at 300 F. for a period of one hour, and finally at 300 F. for a period of one hour under a pressure of from 100 to 300 mm. of Hg. Approximately 7.6 parts of a partially die-chlorinated reactive derivative result. The quantity of glycerine employed may be varied between rather wide limits and a timetemperature schedule other than that indicated may be used. Utilizing 9.52 parts of chlorinated furfural and the indicated time-temperature schedule, the following yields of reactive products result, when one utilizes the following respective quantities of glycerine: Parts glycerine-1.23, 1.84, 2.0, 2.5, 3.0, 3.68, 4.0, 4.5, 5.52; the yield of reactive product equals 7.26, 7.6, 7.7, 7.84, 8.39, 9.10, 9.25, 9.55 and 1057 parts respectively. Reactive products such as the above application, Serial No. 466,480.

Numerous reactive derivatives may be prepared out of the saturated halogenation product of the aldehydes of the mono hetero atomic five membered rings by subjecting the same, or a wide 'variety of derivatives thereof, to electrolytic action in various media.

The saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings as well as the majority of their reactive derivatives may be used per se or in the form of solutions dissolved in stable solvents as. benzene, toluene, xylene, chloroform, ethylene dichloride, trichloi'ethylene, tetrachlorethylene,

monochlorbenzene, etc., etc. In many instances and furthermore quite readily react with the same so that these agents as such do not lend themselves for the preparation of aqueous solutions. On the other hand numerous of the reactive derivatives of the aforesaid halogenated aldehydes lend themselves to the preparation of aqueous solutions. This is particularly true of the reaction derivatives prepared by reacting the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings as well as many of their derivatives (particularly the lower polyethers) with polyhydroxy compounds such as glycerol; 1,2,3, butyl glycerol; 1,2,3, pentanetriol; fl-ethyl glycerol; pentaglycer'ol'; dimethyl pentaglycerol; 1,4,5 hexanetriol;

various haloid esters of glycerol and its homologues; various ,ethers of glycerol and its homologues; nitroisobutyl glycerol; 1-amino-propanediol;, '2i-amino-tert'-butane diol; 1,3-teramethyldiamino-2-nitrop-ropane diol; dihydroxy ketones; diglycerol; polyglycerol; pentaerythritol; sorbitol; mannitol; dulcitol; rhamnitol hepta hydric alcohols; octa hydric alcohols, etc.

.There are other instances where it is desirable toutilize the curing agents in the. form of aqueous dispersions. Itis not practical to prepare such dispersions directly out of the saturated halogenation product of the aldehydesof. the mono hetero atomic five membered rings. However,, such. dispersions may be prepared out of selected derivatives, more particularly those prepared by reacting the aforesaid halogenated aldeh-ydes with. polyhydroxy compounds or polyh-ydroxy compounds containing a' small number of other hydrophilic groups, e. g., amino groups, etc. For this purpose the reaction should be carried out until the reaction products which are usually" initially water-soluble become either partially insoluble in water or substantially wholly insoluble in water. Such products may then be dispersed in water to yield suitable dispersions or emulsions in the usual manner either through theuse-of dispersin agents or stabilizing agents.

As" the reactive polymeric material for use with ther aforedescribed curing agents one may utilize any one of the innumerable polymers which contain the requisite potentially reactive atomic groups in adequate number. Through the teachings of the present invention it is possible to 'procure an almost limitless number of potentially reactive curable polymer compositions from types of polymeric materials that have heretofore been considered uncurable, that i's'in'capable of being converted to an infusible, infusible therlno rigid, or vulcanized rubbery state. Besides the many currently available and well known polymers one may effectively and advantageously utilize the curable polymer made in accordance with the teachings set forth in another of the present inventors copendin applications, Serial No. 495,036.

Essential to the operation of the present invention is the requisite that the organic poly meric material component of the potentially. re

active compositions of the present invention must contain within its structure,' i'. e., have bound to itself, viacovalent bonds, an adequate number of appropriate potentially reactive.

atomic groups. When the alluded to "ap-pro priate potentially reactive atomic groups are presentin adequate number in the structure of the polymeric material the presence of said. groups imparts to the polymeric material. a susiceptance tocurevia reaction with thesaturated halogenation products of the aldehydesof the mono hetero atomic five membered rings and.

their reactive derivatives, so that as a result of the. inter-reactions that occur during the process of cure, the mixture is converted over into aninfusible and insoluble or vulcanized. rubbery state. In the interests of specificness, that portion. of the above referred to appropriate potentially reactive atomic groups which constie tutes the point of. reaction with the referredto halogenated curing agents may be referred to as the appropriate functionally reactive atomic group while the remainin portions onfragments of the group may conveniently be referred.

to asnon'-reactive atomic groups. The: appropriate potentiallyv reactive atomic groups are nothing more or less than the groups known to enter into reaction with the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings and their re-- active derivatives. The groups known to be possessed of the above-alluded to requisitere-- activity are generally and specifically listed in United States Patent Nos. 2,475,801 and 2,490,462

and, for convenience, a detailed listing has-been included in the specifications.

For the purpose of the present invention the term, via co-valent bonds has reference to inter-atomic ties which depend upon the primary valence bonds or forces as distinct. from. the less potent bonding effects due to secondary forces (Van der Waals forces, etc.)

In accord with the foregoing definitions, it. is seen that a potentially reactive atomic group may be divided into two parts: (1) the functionally reactive portion which contains the atoms directly involved in the mechanism of cure and (2.) the non-reactive portion which embraces the atoms not directly participating in the process of cure. In its most elemental form the potentially reactive atomic. group would not include a non-reactive-atomicgroup and thus, by. definition, would;

constitute per se a functionally reactive atomic group. As will be pointed out in greater detail below, of the innumerable functionally reactive atomic groups, the following are the commonestand. best known:

The complexity of the potentially reactive atomic: groups is well. brought outin the list be"- 10W which is purely illustrative and by no means exhaustive.

Using the above symbols we depict below chain.

fragments having attached thereto, via covalent 13 l bonds, potentially reactive atomic groups: (These representations are purely illustrative).

In some instances it is possible to introduce a potentially reactive atomic group of the functionally reactive atomic group type directly into the polymeric structure in the process of polymerization or condensation so that it constitutes an essential linking element of the chain. This possibility is most easily realized only in the case of atoms with three or more valences, e. g., tri-valent nitrogen. Thus, nitrogen permits building a chain structure which comprises elements such as --CNI-IC- as essential links of a linear chain. The superpolyamides (e. g., nylon) are of this type and are susceptible to cure by the referred to halogenated curing agents.

The potentially reactive atomic group may contain within itself virtually any of the known chemical structures. We believe that any organic structure, Whatever its nature, if it can be contained within the potentially reactive atomic group, may be utilized. These same remarks apply to the more detailed or specialized atomic groupings and configurations commonly known as organic complexes, radicals, groups, etc.

The potentially reactive atomic group may embrace aliphatic structures, carbocyclic structures, heterocyclic structures, or various combinations of the same. A wide variety of inorganic complexes may also be included. The potentially reactive atomic group may belong to any one of the following classes as well as to classes not here listed; acetals; acid anhydrides; acid halides; alcohols; aldehydes; amides; amidoximes; amines; anhydrides; azo compounds; azoxy compounds; nitrogenous bases; carbylamines; cyanates; cy ano derivatives; cyclic compounds with side chains; diazoamino compounds; diazoates; diazo compounds; diazonium compounds; disulfidcs; epoxy derivatives; esters, ethers; guanidine derivatives; halogen derivatives; heterocyclic compounds; hydrazides; hydrazine derivatives; hydrazo compounds; hydrazones; hydroxylamine derivatives; imides; isocyanates; isocyanides; iso- Iiit'riles; isothiocyanates; ketenes; ketones; mercaptans; metal-organic compounds; nitriles; nitro derivatives; nitroso derivatives; onium compounds; organometallic compounds; osazones; oximes; oximes of amides; pentazdienes; phenols; phosphorous compounds; quinones;

semicarbazones; sulfides; sulfones; sulfonic acids; sulfoxides; tetrazanes and tetrazones; thio' acids; thioaldehydes; thiocyanates; thioketones; thiols; thiones; triazenes; urea derivatives, etc.

The potentially reactive atomic groups. may embrace one or more of any of the well known organic radicals. Any of the known radicals may be included. The following radicals, listed alphabetically (where more than one term is in use for a particular radical, each term is listed separately), are typical: acenaphthenyl; acetamido; acetenyl; acetimido; acetonyl; acetonylidene; acetoxy; acetyl; acetylene; acridyl; acrylyl;

adipyl; alanyl; aldo; alkoxy; alkylthio; allyl; callyl; amidoxalyl; amino; amoxy; amyl; tertamyl; amylidene; anilino; anisal; anisoyl; anisyl; anthranilo; anthranoyl; anthraquinonyl; anthryl; anthrylene; antimono; antipyryl; arseno; arsenoso; arsinico: arsino; arso; arsono; arsylene; arsaryl; asparagyl; aspartyl; azimino; azido; azino; azo; azoxy; benzal; benzainido; benzenyl; benzidino; benzilyl; benzimidazolyl; benzimido; benzofuryl; benzohydrylidene; benzopyranyl; benzoxazolyl; benzoxy; benzoyl; benzoylene; benzyl; benzylidene; bip-henylene; biphenylene-disazo; bornyl; boryl; bromo; l-butenyl; Z-butenyl; S-butenyl; butoxy; butyl; sec-butyl; tert-butyl; butylene; butylidene; butyryl; camphanyl; camphoroyl; camphoryl; camphorylidene; caproyl; capryl; caprylyl; carbamiclo: carbamyl; carbanilino; carbazyl; carbethoxy; carbomethoxy; carbonyl;- carbonyldioxmcarboxy; carbyl; carvacryl; catyl; chloro; chlorcmercuri; cinnamal; cinnamanyl; cinnamyl; cinnamylidene; citral; cresotyl; cres oxy; cresyl; cresylene; crotonyl; cumal; currienyl; cumidino; cuminal; cyano; cyclobutyl; cyclohexadienyl; cyclohexadienylidene; cyclohexenyl; cyclohexyl; cyclohexylidene; cyclopentenyl; cyclopentyl; cyclopropyl; cyml; 2-p-cymyl; 3- p-cyn1yl; desyl; diazo; diazoamino; diazoxy; dithio; duryl; clurylene; epoxy; ethene; ethenyl; ethoxalyl; ethoxy; ethyl; ethylene; ethylenedioxy; ethylidene; ethylidyne; ethynyl; ethynylene; ienchyl; fluoro; fluoryl; fluorylifdene; formamido; formazyl; formyl; fural; furfural; furfuryl; furfurylidene; Z-furoyl; 3- furoyl; furyl; furylidene; geranyl; glutaryl; glyceryl; glycolyl; glycyl; glyoxyl; guaiacyl; guanido; guanyl; halogeno; hendecyl; heptyl; hexadecyl; hexyl; hippuryl; homopiperonyl; hydrazi; hydrazino; hydrazo; hydrazono; hydroxamino; hydroxy; imidazolyl; imino; indanyl; indenyl; indolyl; indolylidene; indyl; indylidene; iodo; iodoso; iodoxy; isoallyl; isoamoxy; isoamyl; isoamylidene; isobutenyl; isobutoxy; isobutyl; isobutyryl; isocyano; isodiazo; isohexyl; isoindyl; isoleucyl; isonitro; isonitroso; l-isopentenyl; isophthalal; isopropenyl; isopropoxy; isopropyl; isopropylidene; isoquinolyl; isothiocyano; isovaleryl; isoxazolyl; keto; leucyl; malonyl; menthyl; mercapto; mercuri; a-mesityl; 2 -mesityl; methene; methenyl; methionyl; methoxy; methyl; methylene; methylenedioxy; methylidyne; methylol; naphthal; naphthalimido; naphthenyl; naphthobenzyl; naplithoxy; naphthoyl; naphthyl; naphthylene; naphthylidene; nitramino; nitrilo; nitro; aci-nitro; .nitroso; norcamphanyl; octyl; oxalyl; oxamido; oxyamyl; oximido; oxo; oxy; pentamethylene; pentazyl; pentenyl; pentyl; perimidyl; perthio; phenacyl; phcnacylidene; phenanthryl; phenanthrylene; phenenyl; phenethyl; phenetidino; phenetyl: phenoxy: phenyl; phenylazo; phenylcarbamido; phenylene; phenylenedisazo; phenbenzohydryl;

glutamyl;

15" ylidene; phenylureido; phospharseno'; phosphazo; phesphinico; phosphino; phospho; phosphono; "phosphors; ph'osphoroso; phthalal; phthalamido; phthalidene; .phthal-idy-l; phthalimido; phthalyl; picryl; piperidyl; piperonyl; piperon-ylidene; pivalyl; prolyl; propargyl; prophenyl; propenylidene; propiolyl; propionyl; propoxy; propyl; propylene; propylidene; pseudoallyl; as-pseudodocumylj s-pseudocumyl; vpseudocumyl; pseudoindyl; pyranyl; pyridyl; pyridylidene; pyrimidyl; pyromucyl; pyrrolidyl; pyrroyl; pyrryl; quinolyl; quinonyl; quinoxalyl; salicyl; salicylal; salicylyl; selenino; seleninyl; seleno; selenocyano; selenono; selenonyl; selenyl; semicarbazido; silicono; silicyl; silicylene; stannyl; stearyl; stibarseno; stibinico; stibino; stibo; stibono; stiboso; stibylene; styrene; styryl; succinanyl; succinyl; sulfamino; sulfamyl; sulfhydryl; sulfino; sulfinyl; sulfo; sulfonamido;

sulfonyl; tauryl; telluro; terephthalal; tetramethylene; tetrazyl; thenoyl; thiazyl; thienyl; thio; thiocarbonyl; thiocyano; thiohydroxy;

thiol; thiono; thionyl; thujyl; thymyl; toloxy; toluino; toluyl; s-toluyl; tolyl; a-tOlYl; tolylene; d-tolylene; triazeno; triazinyl; triazo; triazolyl; trimethylene; tryptophyl; tyrosyl; undecyl; uramino; ureido; ureylene; valeryl; valyl; vanillal, vanilloyl; vanillyl; veratral; veratroyl; 'veratryl; veratrylidene; vinyl; vinylene; vinylidene; Xanthyl; xyloyl; xylyl; xylylene; etc.

Many of the above listed radicals may be present in the potentially reactive atomic group as functionally reactive atomic groups. Others are non-functional and may, therefore, be referred to as non-reactive atomic groups. It

becomes clear from the above considerations that a virtually unlimited number of structural possibilities exists. In spite of this apparent complexity in practice the problems reduce themselves to much simpler elements. The following principles constitute a helpful guide in selecting potentially reactive atomic groups: (1) the potentially reactive atomic group should be kept as small as possible, (2) the potentially reactive atomic group should not contain any unnecessary non-reactive atomic groups, (3) the potentially reactive atomic group should as nearly as possible consist of nothing more than functionally reactive groups, (4) the simpler functionally reactive atomic groups are preferred. This includes the radicals OH, NI-Iz, --NH--, =NI-I, CONHz, CSNH2, SH-, SeH, TeI-I, PHz, OX (X equals hydrogen or a metallic element, preferably more electropositive than hydrogen in the E. M. F. series), etc.

The above rules are an aid in the selection of polymeric substances susceptible to cure and suitable for use in the present invention.

Thefollowing summarizations and generalizations are of interest in connection with the structures of functionally reactive groups. (1) With perhaps but a few exceptions functionally reactive atomic groups consist of more than one atom. (2) Usually at least one of the atoms is dior poly-valent. (3) Inasmuch as the majority of polymers are of an organic nature and thus contain a multiplicity of carbon to carbon links, it follows that those atoms that permit of most ready attachment to a carbon atom are most suit able for use. (4) As a corollary to (1), (2), and (3) the majority of metallic elements as well as the mono valent halides are not particularly adapted for use as functionally reactive linking atoms between the polymer and the already referred to halogenated curing agents. (5) Experience' has indicated that the elements,,oxygen.,

sulphur, selenium, and tellurium; of the sixth group of elements as well as the elements nitrogen, phosphorous, arsenic, antimony, and hismuth of the fifth group of elements are preeminently suitable for use. (6) Of the elements listed in (5) only oxygen, sulphur, nitrogen, and

phosphorous are abundantly available at low costs. It is more difiicult to utilize phosphorous atoms as compared to the ease with which nitrogen, oxygen, and sulphur can be used. Of these three favored elements, oxygen, sulphur, and nitrogen, it is found that the nitrogen atoms permit of the greatest variety of structural arrangements followed by sulphur. The oxygen atoms permit of relatively little leeway as regards the construction of functionally reactive atomic groups. In the instance of nitrogen, the following atomic structures are feasible for use as functionally reactive groups:

Nitroso (usually slow) 2. NHOH B-hydroxylamine 3. NHz Amino 4. NHNOz Nitroamine 5. -N(OH)NO N itroso-D-hydroxylamine 6. NHNO Nitrosaminc 7. -N=NOH, NHNO, or N'(OH) ==N Diazo Azo N11 Azoxy (usually slow) 10. JQHNH:

Hydrazin ll. N(NO)NH2 Nitroso-hydraz in 12. N=NNH2 Diazo-amino 13. N=NNH OH Diazo-oxy-amino N Diazo-imido. (usually slow) 15. N=NN N z Diazo-hydrazo l6. NHN:=NNH2 Tetrazone l7. N=N-NHN=NH Bis-diazo-amino 18. N=NN'HN=NNHN=NH Bis-diazo-tetrazone nhunare poss edof 1 an un irable; or whiohil ta es a a st th use. o thisel men n eonstruoti ath unotiena lyr aet ve tomieeroups- O y en. ne o the.mosttd sirah e. e em n s. permits. ofthe protiu on ipnlyz ewun tionall reactive groups. .fir t an oremost o wh ch. s he.-O-H.er un nd tseq ive ente wh ei t e hydr een e la ed. y ametellie; l ment. t th rs. bein he ero ide. orde su er-pe oxide ro ps dn om n t n esre iv er link.- ees- It'is o eesi eto n s neea one dereb e number of functionally reactive g roups which util ze. two r o e oi e r ed e ement ee. oxy e v ulph rz x gen end i reeen; nitrer a n dsulphur; ox n. n tr gen nd Sul hur- (7).1he elements oxygen, nitrogen, and sulphur have been listed as the preferred ones for use in forming un ti a v. e ot e at m group su t.- .eble. f eu t e r n ve n. tehoeld. be, emphasized, however, that virtually all i the other knownelemlents with the exception of, the inert gasescan be. utilized in the cqnstructionpf functionally. reactive atomic groups. Applications occasionally arise where. it; is desirable to utilizeanelement other. than the three preferred ones, notwithstanding, in general, the greater cost and difficulty in constructing'and incorporatingsuch atomic groupings into the polymer. (8) Amongthe favored functionally reactive atomic groups utilizing the above referred to preferred elements are those that have one or more hydrogen, elements attached, directly to the same. As has already been pointed out the substitution of] an element more electro-positive than hydrog n increases the potential reactivity ofthe group. (9;). The element nitrogen permits of the construction of the most reactive groups due to the ease w h h ba c. o a eline t u t eseeh be. me I ene iuh t one ly ct ve atomic groups that are of an alkaline nature enter into moreready reaction. On the other hand the l imate u in u een ine p en al y. inherent in the system of a functionally reactive atomic group, and a saturated halogenation prod not of the aldehydes of the mono hetero atomic five member-ed rings, and their reactive derivatives, as well as the strength of the covalent bond is, practically independent of the precise atoms icontained in the reactive group. Although the element, nitrogen, contributes mostly to diversi when oxygen is used as the interlink. (10) It is noteworthy that many of the functionally reactive atomic groups utilizing nitrogen are quite basic or alkaline in character. On the other hand many of the nitrogen containing reactive groups are virtually neutral in character. Al-

ternatively manyof the reactive groups based upon oxygen are substantially neutral in character whereas others are distinctly acidic. The

susceptance to cure and the mechanism of cure itself appears to be independent of whether the functionally reactive atomic group or, for that matter, the potentially reactive atomic group in =toto, be alkaline, neutral, or acid in character. The alkaline types are the more readily reactive but are. not necessarilyto be preferred inasmuch iaslundesirable reactions may occur.

It. is noted that .notx nir cuently struc ur s based pon sulr.

. roup maybeof a type..-.thatattri ut s to plasma Non-reactive atomic grcupamay .be included for .reasonsthat .are urelyincidental orelse they. may. be,..de1iberately included for. specific. func tional reasons. .Thus, thehnon-reactive, atomc,

cization. solvency. we en epellen .pr per i s. p: tical properties. color. as well a a wide e etyot he phys cal and chemi al, pron xt s v It is. impractical :t listin the. present sp e fieee tion allot thematerials which when eo-valently bound Ltd La polymeric structurejmpart to the same the. requ site ,susceptance to cure and thereby rend r. the. curable p l m r. uit le use. as thew-reactive polymeric, componentof the mpos ions .of he p esen invention. asmuch as the prese eeof 'affunet onally.. eeeti ea omio s 0up in the. n tentiallyc r active at i rou in the deciding factor, in determining whether or not a eivenatomic. roup c nta nedv in a robe: meric material.renclersthelatter, suitable. for use n,v the present; nyentien, We... list belo ypical an representative. atomic ro ps. ruc es. i als. d. c mpounds. hat are. func i nally capable .of reacting withthe saturated. halqgena; o p odu s or the, ldeh o the. ono hetero atomicfive membered rings and;their re;- active derivatives. When such. structures are pr t av pol -m n nadequate. qnant ies he latter. can, be cured to an infusible, influsible he m i id o e ou enize t oeryv tate th ou h the; s o ebo e e erred to halo.- ee tion. n e e sae curing. gents. t w lehe se ved ha n. m ny. tance he truc ures listed be ow. e. of; a ompl x. pe. andithat; n e e y. the e are present, a oms and mo: leouler em ntst etere aps non-reae v o r s ire t nter-men io with. he ea y l ude to e oeene ion duct are o rned,- Howeve due o e onda y f cts. he, re en e o een Seemi ly. n n-re ot ye roup$ ofte exer a. pr oun ef eet'u on the un na y react ve tomic r ups-t a direc ly engage in the reaction. soth tt e structural, unit s a, hole ec mes e o edvwithp ope t es hat are new and novel and distinct from thosegof h re-e v r act ng nnet nei r up. con.- s er d. Den e, she' v y wa o ex mp the al.- e o e @Hlemun s innet ona l react ve ato ic u or t e urp es "of: the re n e t nhe ar -r sy. gr up. in Q s. a we known more. ao dio n c a a t r ha he lee el e (OH). r up. o n e. Step: u her nd et eeh ne he ele tr ne at ve mi e up 7 5 .0 1 he aroma tins. e u t n a om oun as s ve mor a ic. n; each instance. neither the phenyl nor the nitr snoo directly en a e, r eeti ns of. ne tralizati nyet t e manifestl e er an effect up n the. reae y- In a. e fec y analo ou ma ner the presence. of atomic oups tha do not. dire tly engage in reaction with the alluded to halogenae t on pro uet disassoeia ne the secondary e f t fr m e pr mary. effect that it has been thought best to list, the atomic groups, structures, radicals, and compounds in the manner indicated. .As. an aid in selecting functionally reactive structures we have noted those that are. comparatively slow or mild in their reactivity. For convenience the materials are. listed according to their. chemical inter-relationships (where more than one. term is in use for a particularamaterial, each tennis listed separately): alcoholic hydroxy; phenolic hydroxyl; amino; sulfhydryl; selenohydryl; tellurohydryl; mercaptan; thiol; .thio ether; sul- 'DhOIliC;

kylamines with aldehydes;

19 phonium; sulphoxide; sulphone; alkyl thiosulphuric; alkyl thiosulphonic; selenomercaptan; selenide; selenite; telluride; dialkyl itellurium oxide; dialkyl tellurone; nitrohydroxy; nitroamino; nitroso; nitro nitroso; alkyl ammonium; acid amide; isocyanates; 'isothiocyanates; isonitriles; primary amine; secondary amine; tertiary amine; tetralkylammonium base groups; unsaturated amine and ammonium-base groups; n-halog enalkylamine groups; thiodialkyl amine; alkylthionylamine; thionyl dialkylamines; alkyl sulphamides; dialkylaminochlorophosphines; dialkylaminoxychlorophosphines; dialkylaminosulphochlorophosphenines; the arsenic, .boron (usually slow) and silicon (usually 'sloW) derivatives of secondary amines; nitroso amines; nitrimines; alkyl hydrazine; nitroalkylhydrazine; alkyl diazo; alkyl diazomides; diazoamino; tetralk-yltctrazone; alkyl and hydroxylamines; trialk-ylamine oxides; nitroso-,B-alkylhydroxyamines; phosphines; primary, secondary and tertiary; alkyl phosphonium;- alkyl phosphinic; alkyl phosphine oxides; alkarsine; trialkylarsine; alkylarsonic; monoalkylarsine'; 'dialkylarsine; cacodylhali'des; quaternary alkylarsonium; tertiary' stibenes; trialkyl stibene oxide; trialkyl stibene sulphide; trialkyl stibene halide; quaternary stibonium; tertiary-bismuthines; alkyl bismuth oxide; alkyl silicane; trialkyl silicon alkoxides; hexa alkyl silanelusually slow); dialkyl silicon oxide; alk l derivatives of germanium; alkyl derivatives of tin, e. g., dialkyl tin, tetra-alkyl tin; hexa alkyl stannane (slow) alkyl stannonic, alkyl tin tri halide; alkyl derivatives of lead, e. g., tetra alkyl lead, tri alkyl lead halide; alkyl derivatives of boron; alkyl derivatives of aluminum, e. g.,' tri alkyl aluminum; aluminum alkoxides; tri alkyl thallium; tri alkyl thallium; thallium di alkyl halides; alkyl derivatives of beryllium; alkyl derivatives of magnesium; magn'esium di alkyls; magnesium alkyl halides; alkyl derivatives of zinc; alkyl derivatives of cadmium; alkyl derivatives of mercury; mercury alkyl halides (slow); alkyl derivatives of calcium; aldehyde; many thio aldehyde structures; halogen substituted aldehyde'(sloW); aldehyde peroxides (slow); alcoholates; acetal (slow); aldehyde di halides (usually slow); most sulph'urderivatives of the saturated and unsaturated aldehydes (slow) including thio aldehydes (slowiand their sulphones (slow); sulphoxides (slow); sulphenes of the trithioaldehydes; mercaptal; hydrox suldi sulphonic acids of the aldehydes (slow) structures derived from ammonia and alaldoximes; diazo paraffins; hydrazones; azines; aldazines; phenyl hydrazones; ketone. (slow) many of the halogen substitution products of the ketones (slow) many ketone acetals (slow) and ketone halides (slow);

many sulphur derivatives of the ketones (usually slow), e. g., mercaptoles; many nitrogen derivatives of the ketones, e. g., hydroxylamine derivatives; hydrazine derivatives; ketone phenylhydravery slow) salts of carboxylic acids or their suliphur equivalents (usuallyslow) per acids (slow) acyl peroxides (slow); thio acids (slow); amino thio acids; acetyl sulphides (usually slow); -'di thio acids (usually slow) primary, secondary and tertiary amides; acid hydrazides; acid azides -(usually very'slow) ;amido chlorides, 'imido chlo- 20 rides; amino-ether; thiamid e thio -imido I ether imide; amidine; hydroxamic' acids and-their chlorides; amidoxime; hydroxamic oxim'es; nitrosoximine; glycol unsaturated glycol: glycol ethers, e. g., glycol amino ethyl ethery cyclic' ethers of the glycols semi esters of glycols; sulphur derivatives of glycols including themercap tans; sulphides; sulphurans; cyclic sulphides; sulphonium derivatives; 'sulphones includesthe' open chain and cyclic types, etc.; nitrogen'derivak tives of the glycols, e. g., nitroso'derivatives; nitro derivatives; their amines and ammonium compounds, e. g., hydroxyl alkyl amines; dialkyl imineoxide, mono alcohols; halogen alkylamines; alkylene diamines; cyclic imines; e. g., alkylene monimines, including the piperidine derivatives; hydroxy aldehydes; nitrogen derivatives of'the hydroxy aldehydes' including the nitro and amino aldehydes; ketone alcohols, e. g., 1:2-ketol,-1:3 ketol; olefin ketols; nitrogen derivatives of ketols, e. g., nitro ketones (usually slow) and amino ketones; many di aldehydes (usually slow) ketone aldehydes, and'di ketones, and most of their nitrogen containing derivatives as well as sulphur equivalents (usually slow), e. g., the monoxirnes, isoxazole; alpha dioximes; etc.; hydrazine; hydroxy acids and many of their derivatives includiing'the acid esters of the hydroxy acids; halogen hydroxy acids; many gamma and delta hy droxy acids and their cyclic esters; the 'laotones (usually slow); sulphur derivatives of thehydroxy acids, e. g., mercaptan carboxylic acid (usually slow); sulphide (usually slow) dicar boxylic acid (usually slow); also the selenides'; most of the nitrogen derivatives of the hydroxy acids including the hydroxylamines or hydroxylamides; alpha hydroxy-imidohydrines; hydra zides of the hydroxy acids; amides of the hydroxy acids; nitriles of the hydroxy acids; aide; hyde cyanohydrins; ketone cyanohydrins; amino acids; polypeptide; lactam (slow); the unsatfurated hydroxy acids and their derivatives corrje sponding to the aboveym'ost of the aldehyde acids (usually slow) and many of their deriva tives particularly those of nitrogen; manyvof the ketone carboxylic acids (usually slow) and their derivatives particularl those of nitrogen; a'ceto acetic acid (usually slow) and its homologu'es as well as many of their derivatives, e. g., phenyl methyl pyrazolone; various carbonic acid derivatives, e. g.,-thio carbonic acid (slow), sulphothiocarbonic acid (slow); trithiocarbonic chlorides of sulphocarbonic acids (slow); salts and esters of the sulphur derivatives of ortho carbonic acids (usually slow); amides of carbonic acid; e.,g. amino-formic (carbamic) esters, e. g. urethane; alkyl urethane; alkylidene urethane; di urethane; nitro and nitroso urethane; urea chlorides; vurea and many of its derivatives, e. g., alkyl urea; ,cyclic alkylene urea derivatives; nitroso ureas;

ureides; ureides of hydroxy acids; hydantoin;

acid; derivatives of pseudo thio carbamide, tc;

guanidine and its derivatives, e. g., nitro hydroxy and amido hydroxy guanidines and their transposition products; many nitriles (usually very slow) amides of carbonic and thio carbonic acid; many oxygen; derivatives. ofcyanogenand their :isomerides (usually: very slow) rcyanuric acidrand itsulalkylic derivatives .(usually'. very; slow) sulphur compounds (if-cyanogen vandslits: isomers: .(usually v'eryeslo'w); mustard oil :groupsv (usually :very slow); icyana'mide (usually very slow) and the amides of-cyanuric acidysmanybfs' thelclerivatives of: dizca-rboxylic a'cids particularly the hydroxyand amino productsptrixhydricalso-1 holicl structures .and mostwof their derivatives which leave at leastonexhydroxyhgrouprfreeuor. which-contain groups'such as the amino etcrergw tetra methyl ,diamino betamitropropane; di-ihyes droxy aldehydes di hydroxy ketoiiesglhydroxya di aldehydes ,hydroxy laldehydeketo'nes "hy'droxy: di ketone; di aldehyde ketone u'suallyvery'slow) aldehyde di ketone -(usually very s1ow );.tri-ketones (usually slow) pdi hydroxyamino carboxylic acids; amino hydrox'y carbdxylicacids'; diamino carboxylic acids; aldo carboxylic acids (usuallyveryrslow) and hydroxy lietc 'carboxylic acidspal dehydo keto-carboxylic acids" (usually very slow) di: keto carboxylic acid (usually very slow) hydroxy' di carboxylic acids; aldo dicarboxylic acids (usually very slow)"; ketone-dicarboxylic' acids (usually very slow) uric acid and --most of its derivatives; tetra hydric" alcohols and various: of their oxidation products and derivatives particularly those containing nitrogen; compounds; containin five or more hydrox y groups -as'wellas most of their derivatives particularly museumtaining nitrogen.- A

' ='It-will be observed that many of thestructur'es embraced by the radicals-,- groups or co'mpounds inithe foregoing list are of an aliphatic charaicter. Of equal import; however, :are' the corresponding carbocyclic and heterocyclic compounds which, dueto space limitationspa're not here specificallylisted. Included in this cat'e'g oryare functionally reactive compounds analogous to the foregoing aliphatic materials but derived from or belonging to one or more of the following classes ofcarbocyclic compounds: tri, tetra, hepta, octa, and nono-carbocy'clic compounds or morespecifically, mononuclear aromatic substances derived from benzene, halogen derivatives of the benzeneh'yd'rocarbon, nitrogen derivatives of benzene hydrocarbons, aromatic compounds of phosphorous, arsenic, antimony, bismuth, boron, silicon, tin, phenyl metal derivatives; sulphonic' acids; phenols; quinones; phenyl paraflinalcohols andtheir oxidation products including the 'monohydric phenyl paraffin alcohols and'their oxidation products; derivatives of i the aromatic amino car boxylic acids; substituted aromatic monocare boxylic acids; mono hyd'ric oxy phenyl paraffin alcohols and their oxidation products; polyhydric aromatic alcohols in which only one hydroxyl is present in each ,side chain sandtheir' oxidation products; aromatic polyalcoh'ols containing more than one hydroxy group in the samelsidechain andtheir oxidation products; mononuclear aromatic substances with unsaturated side chains; hydro aromatic substances with single nucleus; h ydroibenzo derivatives; terpenes; aromatic hydrocarbons containing several nuclei including the .phenyl benzyls and Lthe :polyphenyl'iatty hydrocarbons; e. g., phenyl benzene groups; benzylbenzene group, triphenyl methane group; ,phenyl derivatives of triphenyl carbonyl; phenylbis diphenyl methane; tetra phenyl methane .homologues; di and polyphenyl parafiins; aromatic hydrocarbons of the condensed, nuclei :type includ-ring the indene and hydro .indenegroups; the naphthylene, group; the phenan-thracine group; the fluorene group and the anthracenelgroup.

a ,InaHan analogous mannerlcompounds corre-, sponding ,to the aforementionedv aliphatic, sub: stances ,but derived :from one; or more of th following heterocyclic compoundsmay ,be utilized.

r Here, we, include rings with. an oxygen membeig,

ringstwith asulphunmember; rings with ,one. nitrogen member, rings with two nitrogen mem hers, rings withlan oxygen and a nitrogenmemher, three; 'membered heterocyclic substances,

, four member-edzheterocyclic substancesnfive mem-s bered heterocyclic substances, andsix membered heterocyclic substances More, specifically; maybe mentioned the .three membered heterocyclic, compounds including the mono hetero atomic three \membered rings ,andhthe ,di hetero atomic, three memberedrings; fouramembered hetero 1: cyclic substances including; ;,the mono hetero atomic four memberedrings and-the dirhetero atomic four membered. rings; five memberedhetero cyclicsubstances including. the mono hetero atomic five-membered rings embracing the. furane *group rthiophen group, selenophen group; pyrrole group; benzo furane group, benzo thioe phen group; benzo pyrrole or indene group ine eluding the hydro indole derivatives, di' benzo' turaneior diphenylene oxide group; dicbenzo' thiophen or di phenylene :sulphide groupg. di benzopyrrole, di -phenylimine or carbazolegroup; poly :hetero atomic five membered rings include ingwthe pyrazolexgroup, indazoles, isoxazole group, indoxazen'e or benzisoxazole group; glyoxalines; benzo glyoxalines oxazoles, benzoxalines, oxaA- zoles; benzoxazoles; thiazoles, benzothiazoles,=osotriazoles, pyrro-"(ABl-diazoles; sym-triazoles fu razans, azoximes,oxydiozoles, furo- (AB) -diazoles, thio-(AB) -diazo1es, -thio-(BB)-diazoles, thic- (AA) -diazoles, thio- (ABB) -triazoles, -tetrazoles;' six mem'b'ered heterocyclic compounds including six-membered rings Withan oxygen membergsix mernbered rings with asulphur member, six menubered rings containing a nitrogen member include in'g the pyridine group quinoline group, condensed quinolines; isoquinoline group, phenanthridine naphthyr idines, nBJDhthinOllH-BS, quindo-lines, acridine g'roup, anthrapyridines; the synthetic equivalent of the vegetable alkaloids poly hetero atomic six meiirbered rings including the oxazine's', th i az'ines, d i'az'ihe's; triazine's, 'tetrazines, poly heteroatomi'c slx membered rings containing oxygen and sulphur member; seven, eight and many 'memberedheterocyclic substances. v functionally reactive atomic group may all oneand the same time partake of theattributes associated with m'or-efthan one class of com pounds,-thus itm-aybe inorganicysaturate r all-- pliatic, unsaturated aliphatic, carbocyclic, -heterocyclic, aliphatic 1 plus carbocyclic, aliphatic plus lit'rocyclic car bocyclic plus heterocyclic; or an phatic plus carbocyclic plus 'heterocyclic, etc. The vast majority of the metal-organic fstruc tu r'es behave as functionally reactive atomic groups. This includes the metal-organic com pounds of ammmum, antimony, arsenic, be'ryl'li uni; bis'muth,b0ron, cadmium, calcium; cobalt; co pengauiumgermamum, gold, indium; lantha numy-lead, lithium, mercury, neodynium, -'=po"tassiurn, rhenium, silicon, sodium, tellurium, thallium,,tin, zinc. Experimentation has shown that the metallic compounds in the nature of salts or oxy5derivatives-,e. gi of carboxylic acids or their equivalents, alcoholic (OI-I) groups, phenolic (OH) groups amino'lgroups, etc, in allbftwhich instances the zmetal element has, replaced :a 'hye drogen atom, (active hydrogen) the resultant T5 substance1is usuallymorereactive,thamtheioriee tion products of the aldehydes V 'ofthemono.

hetero atomic five 'membered rings; structures such as --CH2ONa or (CH2O) 3A1; react much more readily and vigorously (sometimes almost explosively).

It'is noteworthy that. the inclusion of appropriate' aromatic nuclei permits of atomic ar-i rangements that have no counterpart inthe field of aliphatic compounds. Included in this" category are' types of diazo' and'diazonium struc-' tures as well as iodoso, iodoxy, and iodonium hydroxide groupings, all of which for the purpose of the present invention behave as functionally reactive atomic groups; 1 1

One may conveniently'divide the polymeric substancesxsuitable for use'in the present invention into two groups. The one group would comprise the manycurrently available and'well known curable polymeric materials. The other groupwould comprise polymeric materialsthat.

have been rendered susceptible to'cure after the manner outlined in copending application, Serial No. 495,036; In the interest of clarity we list below polymeric materials iallinginto the" aforementioned .respective groups. Among the products that fall into the group. comprising, the polymericmaterials that have been, rendered susceptible to. cure. per the disclosures of the copending patentgapplication, Serial No. 4955036, and which are suitable for, use in the present invention are those obtained from the polymerization products (homo-polymers; hetero-polymers, copolymers, inter-polymers, etc.) derived from one or more of the following materials: 3 Ethylene; propene; butenes; pentenes; hex:- enes; allene; butadiene; butadiene, homologues; butadiene derivatives isoprene; piperylene; acetylene; propine; vinylacetylene ,(1-butene, -ine1 3); divinylacetylene (l,5-hexadiene,p ine- 3) and derivatives; cyclop entadiene; ,cyclohexene; cyclo-, hexadiene; styrenes; methylstyrene 2 -pheny lpropine l) styrene homologues; styrene; substitution products; propenylbenzene;, allyl benzene; methyl-vinylbenzene; divinylbenzene; indene; phellandrene; pinene; cedrene; dihydrojnaphthalene; tetrahydronaphthalene; alpha: vinylnaphthalene; coumarone; the vinyl halogenides; vinyl chloride; vinyl'bromide; allyl chloride; allyl bromide; chlorcprene (Z-chloro-butadiene-L3) homologues of chloroprene; bromoprene; chloro derivatives of divinylacetylene; 1, 1 dichloro-ethylene; 1,2 dichloroe-butadiene-lfi; 2,3-dich1oro-butadiene 1,3 1-2 ,3 -trichloro-bu tadiene- 1,3; vinyl ethinyl carbinols; ethylene oxide; divinyl ethers; vinyl alkyl ethers; vinyl allyl 'ethers; 2-methoxy-, ethoxy-, andqbutoxy butadiene-l,3; p-vinyl-anisole; anethole; 1,1- phenyl-anisylethylene; divinyl sulphoxides; di vinyl sulphone; 2 -furfurylmercaptan; vinylamines; isopropenylaniline; aldehydes; glyoxal; methyl'glyoxals; acrolein; methylacrolein; alkylvinyl-ketones; propenyl methyl ketone; isopropyl methyl ketone; mesityl oxide; cyclohexene oxide; acrylic acid, acrylic esters; methacrylic acids; methacrylic esters; halogen substitution products oi acrylic'acids and its esters; halogen sub-' stitution products of methacrylic acids and its esters; homologues of acrylic acids; homologues of methacrylic acids; derivatives of acrylic acid; derivatives of methacrylic acid; vinyl acetic acid; allyl acetic acid; undecylenic acid and its esters; sorbio acid and its esters; vinylpropiolic acid;

vinyl esters; vinyl" acetate vinyl cyanide: 'acryl-r ates; haloacrylatesj esters of eleostearicnacidp 9,11-' and9,12-lin0leic acid; muconic acid, its esters and derivatives; 2s-butadienyl formate; 2-

butadienylacetate ;& 2-butadienyl propionate; '2'- butadienyl' butyratepZ-butadienyI esters; cinnamic 'acid and its esters; butadienyl-2-halo esters; 'e-cap'rola'ctone; ketenes; polymerizable'.

organic compounds containing elements such as,

aluminum; antimony, arsenic, beryllium, bismuth;

boron, cadmium, germanium; lead, mercury,: trogen, phosphorus; selenium; silicon; sulphur;- tellurium, thallium; tin; etc.; cyanogen. chloride; fiuoroni-:.

phosphorus chloronitride; phosphorus tride; silicic acid esters; etc.

Polymers rendered susceptible to cure via the aforesaid invention but procured throughthe process of condensation as distinct from that'of polymerization are also suitable'for use in. the present invention. Such condensations may be of the type-referred to as isopolycondensations: or as heteropolycondensations. These 'polycon densates may be in 'theform of linear chains'or they may be in the form-of two or three dimen-= sional molecular networks. Representative "ofthe products of this category which'may be rendered curable and suitable for use in the present invention are the polymeric materials that-may be prepared by reacting together mixtures of the following. organic compounds:

Dibasic acids plus glycols, polybasic' acidssplus' glycols, 'dibasicqa cidsz plus 'polyhydroxy compounds; polybasicl acidsi plus polyhydroxy com-; pounds, 'diba'sicacids; 'plusadiamin'es (nylons); polybasicacids plus 'diamines,-dibasic acids plus polyamin'es;polybasic acids plus polyamines, phe-. nols plus aldehydes, ureasplus aldehydes,vmel-.

amineplus aldehydes, etc. 7

Condensation. polymers may also be procured from; a variety of,.biior' poly-functional. com-3 pounds containing atomic "groupings susceptible, to interreaction. ,In-thiscategory may bevin-a eluded many polybasic (preferably dibasic) acids capable of, yielding linear anhydrides; p0lyhy+ droxy -(preferab1y .di-hydroxy), compounds 1ca-i pable 'of yielding linear ,poly-ethers; compounds simultaneously containing acid and hydroxy groups; compounds. 1 simultaneously containing acid and aminjogroups, etc. j Among the. better" known of the. above poly-. meric materials which may be rendered curable and suitable for;use inthe' present invention are the polycoumarones; vpolyindenes; 'polystyrenes polyacrylates; polymethacrylates, e. g., methyl methacrylate; polyolefins, .polyoxymethylenesf polyvinyls, e. ,g., polyvinyl, chloride, polyvinyl acetateyrvinyl acetate chloride copolymer; phenol-aldehyde resins of the Novolak' type;- thermoplastic alkyd'resins; resinous or rubbery hydrocarbon polymers; resinous or rubbery eth ylene :polymers; butadiene rubber; butadie'ne styrene copolymer rubber (Buna S); butadieneacrylonitrile copolymerrubber (Buna N); alkyd resins; nylons; .polyvinylidene resins; organic silicon containing resins; natural rubber; etc.

Note that: before the above polymeric materials are suitable for use in the present invention they must first berendered susceptible to cure, e. g, via the teachings set forth in the already alluded to copending-application, Serial No. 495,036.

- For'the sakexof completeness We wish to state that the above condensation and polymerization polymers may be rendered susceptible to cure and usable in theipresent invention by any of the followingmethodsz-w- J (#The method of producing-polymers curable through the use of thesaturated: halogenation products of the aldehydes of the mono hetero atomic' five membered rings and their reactive derivatives as curing agents from polymers that are normally non-curable, which consists in introducing into the said polymer, via co-valent bonds, potentially reactive atomic groups that are reactable with the said halogenated aldehydes and their reactive derivatives, whereby the thus 'modified polymer is rendered susceptible to reaction with thesaid halogenated aldehydes and their reactive derivatives'for conversion to the cured state, said potentially reactive atomic groups being present in the proportion of at least one such groupper thousand linking atoms of said polymer, ff'lhe method of producing polymers curable through the use of the saturated halogenation products of the aldehydes of the mono hetero fatomic five membered rings and their reactive derivatives as curing agents-from polymers that are normally curable only through the use of agents other than the aforesaid curing agents, which consists hr introducing into the said poly iner; via co-yalent bonds, potentially reactive atomic groups that are reactable with the said halogenated aldehydes and their reactive-derivat ives, whereby the thus modified polymer is rendered susceptible to reaction with the said halogenated aldehydes and their reactive derivatives for conversion to the cured state, said potentially reactive atomic groups being present in the proportion of at least one such group per thousand linking atoms of said polymer.

*The method of producing polymers curable through the use of the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings and their reactive derivatives as curing agents from compounds that normally yield non-curable polymers, which conin introducing into the polymer, via inter- ;polymerization during the process of polymer gro'wth, polymerizable compounds containing potentially. reactiveatomic groups that are, react- ,ab le with the ,said halogenated aldehydes and their reactive derivatives, ,wherebythe polymer is renderedsuSceptible. tol reactionwith the said ,hal9 enated aldehydes and their reactive derivatiyes for conversion tothecured state, said potentially reactive atomic groups being present in the proportion of at least one ,such group per lthousand linking ,atoms of said polymer.

The method of producing polymers, curable through. the use of,thesaturated,halogenation products of the aldehydes of themono hetero ,atemic five,- mem bered rings and, their. reactive derivatives as curing ,agents from compounds that, normally yield ,polymers that are curable vonly through the use of ragents other than the aforesaid curing agents-whichconsists in introd cingsinto the polymer, via ,interpolymerization .during-theprocess ofpoly-mer growth, polymerizable compounds containing ,potentially reactive atomic groups that-are reactable with the said halogenatedaldehydes ,and their reactive der-iv- ;atives,- whereby: the polymer is rendered suscep- -tible to reaction, with the saidhalogenated alrdehydes and; their, reactive derivatives forcon- .yersion; to -the cured; state; said potehtially reac- -tiive atomic groups; being-present dn the proporriliion-pt at least one'such group per thousandlinking atoms of saidpolymer. T

The method of producing polymers curable through the use: of the saturated halogenation products ofithe aldehydes of the mono hetero atomic five membered rings and their raction derivatives as curing agents from compoundsthat normally yield non-curable polymers; which consists in introducing intovthe-polymer; via interpolymerization during the process of polymer growth, polymerizable compounds that are non reactable With the aforesaid halogenated aldehydes and their reactive derivatives and then converting the said polymerizable compounds after incorporation into the polymer, over into the structures containing potentially reactive atomic groups that are reactable with said hal ogenated aldehydes and their reactive derivatives whereby the polymer'is rendered susceptibleto reaction with the said halogenated aldehydes and their reactive derivatives for conversion tothe cured state, said potentially reactive atomic groupsbeing present inthe proportion of at least one such group per thousand linking atomsof said polymer.

,The methodfof producing polymers curable through the use of the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings and theirreactive derivatives as curing agents from compounds that normally yield polymers that are curable only through the'use of agentsother than the aforesaid curing agents, which consists in introducing into the polymer, via interpolymeriza tion during the process of'polymer growth, polymerizable compounds that are non-reactable with the aforesaid halogenated aldehydes and their reactive derivatives and then converting the said polymerizable compounds, after incorporation into the polymer, containing potentially reactive atomicgroups that arereactable withrsaid halogenated aldehydes and their reactive-derivatives whereby the-polymer is rendered susceptime to reaction with the said halogenated aldehydes and their'reactive derivatives for conver- 'sion to the cured state, said potentially reactive atomic groups being present in the proportion of at least one such group per thousand linking atoms of said polymer. i r l -Representative of the 'productsthat fall into the group comprising thecurrently available and 'well known curablepolymeric materials suitable for use in the present invention are the following: phenol-formaldehyde resins; phenol-aldehyde resins ingeneral'j phenol-furfural resins; 'furfural-formaldehyde phenolic interpolymer resins; guanidine-aldehyde resins; melamine-aldehyde resins; resins derived from urethan; resins derived fromacetone formaldehyde condensations; furfur-acetone resins; resins produced ;by reacting aldehydes with polyhydroxy phenols, e. g., resorcinol, catachol, hydroquinone, pyrogal- 101, etc.; various urea resins; alkyd resins derived i from polyhydricalcohols and containing-- free OH groups; in general-resinsproduced by reacting aromatic amines with aliphatic, carbocyclic, or heterocyclic aldehydes, e. g;, aniline-formaldehyde resins; resins derived from cashew nut shell liquid or the-oil of the marking nut; gum accroides and resins derived therefrom; dragon's blood and resins derived therefrom; butadienestyrene copolymer rubbers, e. g.,' Hycar 08-20; butadiene-acrylonitrile copolymer rubbers (Buna N, Perbunan, Hycar OR-l5); shellac; shellac-,derivatives; gelatin; bone glue; hide glue; proteins ,of all types; casein; casein plastics andglues; ,polyvinylalcohol;- poly-vinyl alcohol-acetate; polyvinyl butyral; polyvinyl butyral-alcohol;

catalyst. catalysts.

silk; superpolyamides, e. nylon; cellulose; esters of cellulose such as cellulose nitrate; cellulose} acetate; cellulosepropionate; cellulose butyrate; cellulose nitrate acetate'; cellulose acetate-but'yrate; cellulose acetate-propionate; cellulose-xanthate; etherification products of cellulose; methyl Cellulose; ethylcellulose; benzyl cellulose; propyl cellulose; and in general the'produc'ts resulting from theinteraction of cellulose with alkylating agents such as alkyl halides or 'aryl alkyl halides in the presence of strong al.- =kalies; 'hydroxy ethylcellulose; tosyl cellulose; colored ethers prepared by coupling the amino ben zyl ether of cellulose with diazonium salts; sodium cellulose glycolate; cellulose glycollic acid; cellulose hydroxy ethyl ether; the mixed derivatives of cellulose prepared by reacting the same with an acid anhydride and an aldehyde simultaneously; cellulose acetals; cellulose ether "esters; esterifiedhalf acetals; sodium ether derivatives; cellulose addition compounds; amino cellulose; sodium cellulosate; etc., etc.

Aninspection 'of the products listed in the group comprising the well known andcurrently "available'curable polymeric materials discloses that virtually all-of the known polymeric mater'i'als that contain potentially reactive atomic groups are suitable for use in the present invention." It is also to'b'e'noted that the list covering the group comprising polymeric materials that may be rendered susceptible to cure via the teachings 'of the oopending patent application, Serial No. 495,036 and thus'usable in the present invention is exceedingly extensive. It is clear from the foregoing that a virtually limitlessnumber of polymers may be utilized as the polymeric material component of the potentially reactive.

curable compositions of the present invention.

" In the preparation ofthepotentially reactive curable compositions of the present invention it is often desirable and not infrequently necessary toinclude a catalyst or accelerator. 'For'the sake fof convenience the catalyst or accelerator will hereinafter simply be referred to as the catalyst. The primary purpose of such a catalyst is to speed up the rate at which the compositions 'can be cured at a given temperature. The presence of a catalyst often permits the use of lower action so that a catalyst that is best suited for use in one composition is not necessarily the best for other compositions. In some instances the catalyst serves other purposes besides merely enhancing the speed of the curing reaction. This is particularly true in instances where the catalyst is possessed of pronounced acid neutralizing properties and where the system (polymeric material plus a saturated halogenation product of the 'aldehydes of the mono hetero atomic five memberedrings or their reactive derivatives as curing agent) is one which liberates acidic materials'l" In some instances the alkalinity or the =acid=neutralizing 'abiilty of a catalyst may be intimately related to its ability to function as a Welist below a few representative Ashas already been pointed out, catalysts are more or less selective in their action. Some catat the same time absorb acidic materials and lther'eby'become more or less neutralized Wherea othersenter into reaction-and-appear to instill into the composition an activation energy sufll: cient to initiate a thorough reaction throughout the mass, Very many of the neutral orbasic oxides, hydroxides, etc., of the metallic elements function as catalysts to a greater or lesser degree.

Referring-first to the oxides and hydroxides of the elements of group I as per the periodic system we wish to state thatthose of cesium, rubidium, potassium, sodium, and lithium are not veryefe fective and besides possess numerous objectionable features. The oxide and hydroxides of copper are in some instances very effective. Silver oxide does not appear to be effective and besides is objectionable due to it high specific gravity and high cost. The same remarks are applicable to gold. I I

Experimentation with the elements of group II has shown that the divalent alkaline earth oxides of barium, strontium, and calcium are on the whole possessed of but a moderate activity and are, therefore, not particularly recommended as catalysts. The otherelement of group II, mencury, cadmium, zinc, magnesium, and beryllium are all highly effective catalysts. From a practical standpoint the oxides and hydroxides of magnesium' and zinc, due to their relative abundance and slight or zero toxicity, are particularly recommended. 1 4

None of the oxides or hydroxides of the elements of group III appear to possess an appreciable catalytic effect. Aluminum oxide, however, is very useful as a filler in some of the compositions of the present invention. Other compounds of aluminum, such as technical aluminum stearate, function as blister inhibitors and also as ouring, agents in certain instances (see co-pending patent application, Serial No. 478,120, filed March 5, 1943 now Patent 2,402,075 issued June 11,1946). The oxide of boron, as wellas numerous other of its compounds particularly those of theglycols, glycerols, etc., while not useful as catalysts, none the less are useful as secondary curing aids in certain instances, e. g., polyvinyl alcohol, polyvinyl butyral, etc.

. Of the common elements of group IV, the oxides and hydroxides of tin and leadare possessed of a moderate catalytic effect. The high specific gravity and the toxicity of the lead compounds militates against their use Whereas the tin compounds are possessed of a limited selective activity.

Of the common elements of group V the oxides of arsenic, antimony, and bismuth are possessed of definite catalytic properties though on the whole they are inferior to product such as zinc or magnesium oxide.

Of the common elements of group VI the oxides and hydroxy oxides of chromium are effective catalysts. The other elements are possessed of little, if any, catalytic activity as far the the pres ent invention is concerned.

Of the common elements of group VII only the oxides, hydroxides and basic compound of manganese are catalytically effective.

Of the common elements of group VIII the oxides and hydroxides of iron, cobalt, and nickel are catalytically active. It is interesting to note that of the three elements listed the oxides of iron are the most potent. Red iron oxide is definitely more active than the black iron oxides. It is interesting to note that in spite of the relative stability, neutrality and inertnes of red iron oxide it is none the less one of the most active and p0-v tent of catalysts. v

' erallyr useful catalysts.

amalgam a There ;are indication that: numerous of the rarer eearth elements. are! catalyticallynactiveibut owing to their scarcity: and"highucosta-theytcan hardly'tberecommended for commercial; usage.

Of..thervarious inorganic catalyststhatwe. have mentioned, it is interesting to notefthatrmostrof the metallic elements of series W ofrthetperiodic systemware: catalytically'active although both (titanium roxide and vanadium pentoxidewiare possessedof but aslightactivityw t u .1 w 10f: the' variouselements that weihave listedfwe believe that the oxides and hydroxides; preferably the a former, 1 of the. 1 elements; magnesium,i'%zinc, iron zand copper :arepthe most-reflectiveaandtigene In. manyvinstancesrbest results are procured by utilizing a mixture of catailysts, 'e; g. :MgO'and ZnO; =Mg0ia1id1rFe2'Oz; Mg'O, rZnQFezOyand CuQyset'c. a l 1 C -:There are. few,; if; any; organics material that function in astrictly'catalytic capacity. Virtually aill tiorganic "compounds that-exert lany' measurable effect upon the speed of cure are of ria reactiveunature 2 .and are 1' capable: of -;entering: .intdi'? a ready. reaction lwith thevsaturated rahalogenation products: of uthe. :aldehydes wof'rthe .xmono hetero atomic; five 'menibered ringstand their reactive rde rivativessas curing wagents M'Drganic" fcatalysts. larevprobably "more rproperlysreierred'; to for ganic aids. Organic aidsy-may -bezzdividedrinto two classes. rFirst, thosei that aareypossessed-lof a basic character, usually attributable to nitrogen atoms within the molecules and;second,.=thoseoof a. highly reactive and unsaturated character which contain functionally reactive atomic groups. In thefirst category are included such materials as the organic -amines and organic bases. The secondtcategory includes materials such. asthe aldehydesof the mono hetero-atomic five .membered rings of their. corresponding alcohols, e: g., iufur'al andsfurfuryl alcohol. Cata- ,lytic aids of the first type usuallyffunction by virtue oftheir alkalinity. in that they actias acid acceptors or by reaction with the curing agent generate activation energies that augment the mate of cure. Organic aids of the second class probably function primarily .by virtue of the en ergy liberated upon their reaction-e. g., furfuryl alcohol usually reacts very violently with liberationof considerableheat. v a Theiinorganic catalysts, particularly the oxides of magnesium, zinc, iron; and copper, arefar 'more potent in. their catalytic action than the organicaids.

The quantity of catalyst, if any, to be included in the compositions of the present invention isv governed by a variety of factors, theprincipal of -;.which are (1) the. speed of cure sought, (2') the power or strength of the curing agent employed, (3) .the'nature ofthe curable polymeric material, (4) the temperature utilized in effecting the cure, (5) the type and quantity (if any) of fillers, plasticizers, and softenerspresent in the com- .position, (6) the potency of the catalystinquestion,('7) the particle-size of the catalyst, (8) the thoroughness with which 1'. the ingredients are verylarge quantities'in'whichcapacity they funclit 30 tionbothasc'atalystand asfiller. Broadly speakings there is no limitation as to thecduantitil :of catalystthat may be used. The illustrative, examples givenbelow are indicative of recommended practices. In some instances "catalysts exert untoward effects; (e. g., when copper oxide isused .as a catalyst; andthe composition isiheat'cured-in common steel molds, there is a tendency for copper plating to occur).

In accordance with the teachings of the present invention, potentially reactive curable compositions'maylbe' prepared by mixing together any material for which a'curing'agent selectedfrom the'class comprising .the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings :and their reactive derivatives can be prepared with the aforesaid curing. agent. .The applicants have been able to prepareLcuring-agents selected. from the class comprising the saturated halogenation products .of-the aldehydes of the. mono hetero atomici'five membered rings and their reactive derivatives, which: are; preeminently suited for the curing. of the'xproducts listed in' the following list:

Curing agents vfor phenol-alcohols; curing agents for phenol-formaldehyde resins; curing agents for :phenol furfnral resins; curing agents for wacetone formaldehyderesins; curing. agents for-cashew nut 's'he'll resins; curing:agents*for urea resins; pcuringiagents for thiourearesins; curingxagents for melamine resins; curing agents for furfur-acetonerresins; curing agents foraldehyde resins; curing agentsfor aldehyde-amine resins; curing agents for 'guanidineg resins curing agents for. urethan resins curingpagentsj for: our-- able ethyleneoxide'resins; curingagents for curable olefine resins; curing: agents: forcurable petroleum' res-ins; curing agents-for curablewalkyd resins; curing agents. for. curablecoumarone and indene resins pouring agents for curable drying oil resins; touring: agents -1for curable polystyrols; curing agents for curable acry1ateresins:;. curing agentstfor 'curablec methacrylate resins; curing agents for curable acrylonitrile resins; curing agents for curable polyvinyl ethers; curing agents for curable polyvinyl esters; curing agents for curable: polyvinylwchloride; curing agents forpolyvinylalcohols; curing agents for. animal glues, water .dispersible type; curing agents for animal glues; water; soluble type; curing agents vfor casein; curing or tanning agent for proteins andQalbuminous -material;..tanning agent for, leather; curing .agentsafortshellac; curing: agents forfibrous silks; curingagents for silk solutions; curing agent for W001 solutions; curing agents for. nylon plastics; curingagentsytorwnylon threads; curing agentsfornylon in solution form; curing agents for cellulose; curing .agents for celluloseacetate; curing agents for cellulose propionate; curing agents for cellulose ,butyrate; curing agents for cellulose acetate .propionate; curing agents for cellulose acetate butyrate; curing agentsior cellulose acetate nitrate; curingagents for cellulose benzoate; curing agents for cellulose nitrate; curingiagents'formethyl cellulose; curing agents for ethyl cellulose; curing agents for propyl cellu- 'lose;' curing agents'for butyl cellulose; curing agents for benzyl cellulose; vulcanizing agents for butadieneacrylonitrile copolymer rubber; vulcanizing agents forcurable butadiene-styrenecop'olymer rubber; vulcanizin agents for curable natural rubber-derivatives; vulcanizing agents for curable butyl rubber; vulcanizing agents for polyisobutylene curing agents tor curablebu-tene- -o'lefirie oopolyi'ner rubbers; and resinous" curing "31 agents derived from chlorinated furfural'; curing agents, general purpose; curing agents, water dispersible; curingagen'ts, water soluble; curing agents for polyvinyl acetals; and curing agents for curable-polyvinylidene resins. v

The following examples are cited. to illustrate the production of the potentially reactive compositions of the present invention. The examples are merely demonstrative and are not in any way to be considered as exhaustive. In the interest of simplicity we shall consider first the potentially reactive compositions derived from a single resinous entity or its progenitor. For this purpose we have selected as typical the furfuracetone condensation products. By way of explanation,.it may be stated that furfuracetone condensation products maybe produced by reacting together furfural and acetone in substantially molecular proportions under conditions of controlled alkalinity. The furfuracetone is then condensed by reacting it under alkaline conditions at elevated temperatures. If toward the end of the operation the alkalinity be neutralized, then one ends up with a liquid condensation product. On the other hand if the conditions of alkalinity are maintainedthen an exo thermic reaction sets in towards the close of the operation and a grindably hard resinous product results. Products intermediate to the thinly fluid condensation product and the grindably hard product may be procured by mixing the two materials in any desired proportion.

' We describe below a variety of potentially reactive combinations comprising the afore alluded to furfuracetone condensation products and .a curing agent selected from the class of the fully saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings 'on their reactive derivatives.

' Example 1a.As'co-agent a'grindably hard furfuracetone-resin (22 parts) is melted and mixed with an active curing agent (3.3 parts) prepared by reacting chlorinated furfural with an excess of methanol. I

Example 1b.Similar to Example 1a but utiliz ing the curing agent produced by reacting chlorinated furfural with secondary amyl alcohol. 7 Example 1c.Similar to Example la but utilizing as curing agent the reaction product procured by reacting chlorinated furfural with tetra- 'decanol. i I I g Example 1d.Similar to Example 1a but utilize ing as curing agent the reaction product procured by reacting chlorinated furfural with the mono methyl ether of ethylene glycol. I

\ Example 1e.Similar to Example id but utilizing as curing agent the reaction product procured byv reacting chlorinated furfural with methanol in the presence of zinc dust.

, Example 1f.Simi1ar to Example id but utilizing as curing agent the distillate procured in distilling the methanol reaction product ofchlorinated furfural.

. Ewamplel g.+Sim i1ar to Example 1a. bututilizing as curing agent the reaction product obtained bypartially distilling off chlorinated furfuralin the presence of xylene.

.Example 1h.-Similar to Example 1a but utilizing as curing agent the reaction product procured by reacting th methanol reaction product i of chlorinated furfural with further quantities of methanol. I

lizing as curing agent the-reaction product proforegoing examples.

32 cured byfsubjecting chlorinated furfural flrs't to partially controlledzdistillation' and thenssubse quentlyireacting it with methanol. 1'

Example -1lc.-=Similar' to Example'la but' uti IiZing as: curing." agent the straight, unmodified chlorinatedfurfural.

The products ofthe foregoing illustrative ex-' amples I constitute potentially reactive compositionszthat are; capableof being converted to-ari infusible and insoluble cured state; The prod-Z- ucts maybe converted into the cured state either by permitting them to stand for very long periods .ofitime. at room' temperaturesor :they maybe muchmore 'rapidlycured by subjecting themnto elevated temperatures. At' any given. temperatureit is'possible to speed up or slow up therate .o'f cure through the'use' of appropriate catalysts. It has been found that the rate or. cure depends upon; the. temperature, type of curing. agent used, quantity of curing agent used, type ofcatalys't used,: quantity- .of. catalysts used, the concentration,:the.presence of fillers, the presence of miscellaneous materials such as solvents, plasticiz ers', etc; Also of'importance' isthe age of the potentiallyreactive composition. As a rule more satisfactory cured products result'when the com positions are permittedto imellow or age at room temperature prior to being subjected to =cure--at elevated temperatures. 1 The data presented in Table I illustrates the effect of catalysts upon the compositions of'th'e .IABLEI.

Product Red Iron Magnesia Zinc Cu'riw of fii t. Oxide, (Light), Oxide, oxide, 2 0.73 pt. 0.714 pt Mine. Mina.

3 -11; I 3-ll 1 2 I -3.-1,8 l%- 5- 7-40 2V 7 7'-42 4 7 4 20 2 4 3-31 %,2 "3-30 6 4-17 1 2 3 3 3 7 6-30 1 1-24 Product Antimony Calcium Iron'Oxide Iron 'Zin c of'y xide Oxide, (Black), Powder, Powder, .ll lxan ple 2 61 pts. 0.51 pt 2.07 pts. 0.50 pt 0.,63 pt,

Mins. Mine. Mins, Mine. 24 3 -41 7 -32 1% 8' 20 -47 2 -16 -18 1% 13. -47 5 -48 6Vz-24 1% -13- 16 -60 10 -42 11 -35 2 A-9 18 -65 8 -25 4 -32 2" -8% 14 4 -30. .6 -15 %-5, 11 -30 4 -10 5 -26 io- 20 -53 11 -33 19 -58 13 -30 14 -28 4%19 10 -37 5 -12.

. Ferric Hy-,,. Cupric Product Iron Oxide droxide Cobalt Hydrox- Chromium of (Brown), 1 (Dried Oxide, ide, ,Oxide, Example 0.96 pt. out) 1 49 pts. 0.86 pt. 0.6.0 pt.. 0.96 pt. I Mine. Mine. Mine. Mins. Mins'.

2 -17 1%- 2 6 6%-3l 7 -17 11 1%- 5, 1% 2% 5% -25 4 -15 9%47 2 -15 2 -3 6 -36 5 -15" 15 -60 6 -45 2%! 8 -23 9 -21 "171' -59 3 -14 2 -3 7 -29 9 -19 13 -56 1 -5 1 -2 4 -25 10 -20 6'-40 1' 5 A- M 3 -24 2%-11 Il -34 11 -45 5-14 8 -37 12 -35 34. 3 8 3 3% 11 -45 6 -10 13 -52 %-14 54- :1%-14 1 5 v 7.,-34

TABLE -o ONTIN'UED Product Catalyst Catalyst Catalyst Catalyst Catalyst of 18432-21, 18432-13, 18432- 18432-D, 18432-13, Example lpt. i 1 pt. 1 pt. 1pt. lpt

Mics. Mina. Minx. Mine.

2 -17 1% 4% 3 -13 1%- 2% 1%-27 1.15-10 2 4-11 0. 57-1. 5 1%3l l 20 336-35 344% 254-35 2 -25 2 -23 1% 3% 1%18 1%- 8 2V -22 1%- 2% 154-16 1 4% 1 A- 5 1% 1%15 -10 1%20 1% 4 -32 10 -22 GV -BO 5 3 -28 3 -17 254-16 1%- 2% 3%-12 l V 42 134-10 0.17-0.50

Product Catalyst Catalyst Catalyst Catalyst Catalyst of 18438-14, 18438-13, 18438-0, 18438-D, 18438-1 3, Example 1 05 pts. 1 28 pts. 1.28 pts. 1.28 pts. 1.25 pts.

Mins.

l%- 3 A- 2 1%- 5 l- 5 1 r The quantity of catalyst is indicated in terms of parts used per 14.17 parts of potentially reactive composition. The times as listed in the table denote the time in minutes required for the composition to cure. as determined by smear tests carried out upon asteel hotplate maintained at approximately 310 F. The smaller figure to the left denotes the time required ,to convert the product to, the point of incipient ,infusibility, While larger figure to. the right denotes the time required to convert the product to a hard and brittle state.

Catalysts Nos. 18432-A,,B, C, D and E, a well as catalysts Nos. 18438-A, B, C, D andE were prepared, by mixing together solutions of ferric chloride andzinc chloride in the proportions indicated below and then precipitating via the addition of calculated quantities of a onefnormal solution of. sodium hydroxide. The precipitates were sucked damp-dry upon a suction funnel and dried at a low temperature,

Utilizing. the data contained in basis, we present in Table II a comparison or the reactivities of thevarious curin agents used in preparation of the products of Examples 1a to 1k.

TABLE II 1 Average Cure Average Cure Potentially Reactive Overall Time Using Time Using Compositions Per Summarized the 10 Most the 5 Most Example Cure Time Effective Effective Catalysts Catalysts Mins. Mins. Mine. 6.27 -19.8 1. 65 5. 70 1.44- 3.13 4 715-15. 05 0.907- 3.35 0.83- 1.88 52 -22.7 1.44 6.85 1.44- 3.50 6 56 -26.5 1.825- 6.525 1.81- 4. 31 5 58 20.08 1.75 5.55 1. 63- 3.00 3 65 -15. 90 1. 067- 3.75 0. 94- 2.13 2 83 -12. 25 0.555- 2.65 0.50- 1.06 10 84 -32. 18 5.75 -16. 50 5. 13-14. 75 5.45 -16. 50 2.07 5. 25 1. 74- 2.88 1.615- 8. 90 0.312- 1.207 1 0.20- 0.61

The above data reveals that the 5 most active of the potentiallyreactive compositions us'edlall in the following order: 170 (most active),.lg ,,1oj,

assume.

1i and, 1a. (least active of the 5). Table II also.

A L II Average Cure 1 i i Time Using the Catalyst Compositions 5 Most Active 1a to 1k Compositions Mics. Mina. Red'Iron Ox de 16. 5 47. 1.10- 2.75 Magnesia (Light). 146. 5 -457. 0 10.90-33.00 Zinc ()xide 24.25- 62.9 1.35- 3.18 Cupric Oxide"... 52.0 279. 0 3. 80-26. 60 Antimony Oxide. 202.0 -521.0 13.2 -32. 20 Calcium Oxide 155. 50-4460 12.9 -35. 20 Iron Oxide (Black). 52. 2 276. 0 3. 03-16. 80 Iron Powder 83. 5 -300. 0 7. 20-23. 80 Z1110 Powder 27. 6 89. 25 1.43- 4.15 I1'on Qxide (Brown) 32. 75-173. 0 1. 55- 7.40 Ferric Hydroxide (Dried out) 19:25- 37.0 1. 20- 1. 90 Cobalt Oxideflc. i 60.5 -289.0 5. 00-26. 60 Cupr c Hydroxide 73. 50- 18.00 4. 70-12. 20 Chromium Oxide 161. 50-514. 00 9. -41. 40 15.12- 38.92 0. 62- 1. 53 26. 25-257. 00 2. 20-19. 60 28. 65-151. 00 1. 28-10. 70 30. 50-200. 00 1. 80-12. 40 15.49- 35. 50 0. 65- 1.50 18.00- 65. 50 0. 9 3. 40 15. 42-12800 0.88- 8.80 15. 42- 63. 50 0.7 3. 30 17.75-137.00 1.05-10. 20 17. 45- 45. 50 0.89- 1.90

1 r TableI asa The above table discloses that of the 24 catalysts used; the .10 ,mostactive are (listed in, the order of decreasing, activity): No.,18432-E; No. 18432-AyNo. 18438-E; ,ferric hydroxide (dried out); iron oxide, red; zinc oxide; No. 18438-0; No. 18438-11; Zinc dust; 18438-3.

In Table IV are presented the cure times procured when utilizing the five most active of the potentially reactive compositions and the .three most. potent catalysts.

TABLE IV Potentially Reactive l i C 1 C Compositions per ata yst ata yst atalyst example 18432 A 18432 E 18438-E Mina. Mins. Mine.

The applicants have found thatin the instance of furfuracetone condensation products zinc oxide (probably admixed with more or less zinc hydroxide) prepared atlow temperatures is one of the most effective catalysts. For this purpose 5.10 ounces of zinc chloride are dissolved in water and the volume made up,to one liter. A NaOI-l solution is prepared by dissolving 1.48 ounces of sodium hydroxide in water and making the volufrn'eup wane liter. ,Sodiumhydroxide solution, in quantities sufficient to react with the chloride ,ions is'added to the zinc chloride solution.{fThe precipitate is allowed to settle and then transferi edljto a suction filter and washed. The washedprecipitate i's sucked to a damp-dry condition on, afilter'and. is'then broken'up and dried "at'a temperature of between 200 F. and

c 1 meta-benzine disulfonic acid- F". under a inch vacuum. dried pi-ad TABLE v Potentially Reactive Compositions Catalyst No. 23,510, Parts per 14.17 pts. of composition The times indicated denote the time required to cure the: potentially reactive mixtures to'the point of brittle hardness, as determined by smear tests carried out upon a steel hotplate maintained at 310 F. y

The above table discloses the interesting fact that as the quantity of catalyst is increased the v 4 speed of cure is likewise increased. Beyond a certain point, however, increasing the quantity of catalyst tends to slow the reaction. It appears that there is a certain optimum quantity of catalyst for each specific potentially reactive composition. In the instance at hand it appears that the use of 0.50 part of catalyst 23510 per 14.17 pts. of composition yields the fastest cures.

Many organic compounds, particularly those of an acidic character, function as eifective catalysts or co-agents. The data presented in Table V1 is representative of the effect of such compounds upon potentially reactive compositions consisting of 'furfuracetone condensation products as co-agent and fully saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings or their active derivatives as curing agent.

TABLE VI Agent Remarks maleic acid speeds up cure. phthalic acid Do benzine-sulfo a marlfiedly speeds up cure, V o.

sulfanilic acid chromotropic acid d1chloro-succinic a tartaric acid speeds up cure.

o. markedly speeds up cure. slight efiect.

ptoluenesulphonyl chloride speeds up cure.

benzo-trichloride speeds up cure; also good solvent. a-hydroxy-iso-butyric acid little effect. methylene dianilid markedly slows up cure.

aniline o. a-nitro-napth little effect but good solvent. maleic anhydride speeds up cure. succinic anhydride. Do.

As exemplified by the above tabular data we have considered a constant ratio by weight of active curing agents to the quantity of furfuracetone condensation product. We wish to emphasize thatthe ultimate properties of a potentially reactive composition are markedly influenced by the ratio of active curing agent to its co ag e'nt. The results listed in Table VII may be considered as representative.

stasis TABLE VIII Furfur- Curing Composition 233% Agent Condition after standing 24 hours Number safion N 0. at room temperature product Pm. Pts. 29836-11 8 16 firm, tough gel. 29836- 8 12 similar to A" but slightly-softer. 29836-0 8 8 similar to F but wetter. 7 29836-1)... 8 6 pis tyI-wet type of gel, softest-of e 01;. 1 29836 E 8 20 slightly softer than B." 29836- 13 8 24 slightlysofter than E but drier. 29836-G...- 8 r 32 softer than F and dry. I

Curing agent No. 17792, referred to in the above table, designates the product resulting from the interaction of methanol (in excess) with ch10 rinated furiural.

Table VII discloses the interesting fact that if we keep the quantity of furfuracetone condensation product constant (8 ounces) then the most active composition results when we use 16 parts of curing agent. When the quantity of curing agent is either increased or decreased beyond this point the rate of cure, as determined by the firmness of the resultant irreversible gel, diminishes.

It is to be noted that whereas the product of examples la to 1k contain but 15% of curing agent on the weight of furfuracetone condensation. product, the products of .Table VII contain anywhere from 75% to 400% of curing agent on the weight of furfuracetone condensation product.

As little as one tenth of one percent of curing agent oftentimes'manifests its presence by e'xert ing a measurable effect upon the composition. It is significant that inmany instances the curing agents around which the present invention centers can be utilized in proportions from as low as one tenth of one percent to as high as several hundred percent to yield compositions of industrial interest.

A very significant point disclosed in the above tables resides in the fact that the ratio of time required to reach incipient infusibility to the time required toreach the point of brittle hardness can be varied over rather wide limits. It would atelier from this thatthrough-the proper selection of the quantity and type of curing agent, as Well as the quantity and type of catalyst, it should be possible to obtain any desired or predetermined cure curve (1. e., state of cure versus time) The cure curve plays a very significant role in'the'manufacture of coating compositions,

molding compositions. etc.

Not infrequently fillers exert a profound effect upon the potentially reactive compositions of the present invention. It is found that some fillers tend to speed up the rate of cure, whereas others slow it down. Some fillers tend toward the production of compositions that are porous whereas others yield dense and substantially non-porous products. The datapresented in Table VTlIis typical.

In preparing the mixtures to which the filler was added, parts of liquid furfuracetone condensate were mixed with parts of curing agent No. 17792 along with five parts of commercial zinc oxide. The mixtures were ballmilled for a period of not less than 3 hours. Filler was added in the proportion of sp. grav. 1X 1.80 parts'of filler to '3 parts of the above mixture so constant.

TABLE VIII (lured in 140 F. oven Cured in 200 F. oven Number ofMix Flue Time Poros-, Hard Time Poros- Cured, ity Hess Cured, ity Hardness Days N o. Hours "No. 1

29,704-A... hydrated alumina 3 7 H 2% 6 H+ 29,704- 2 4 H+ I 6 11+ 2 10 H 8 13+ 1 4;, S1 V l H+ 4 2 SIS 2% 10 11+ 4 2 H 2% l0 H+ asbestos flour 9 VS 5 8 H+ urea formaldehyde condensate 4 8 H 2% 8 EH- titanium dioxide 1 2 11+ 2V 4 H+ calcium carbonate 8. 6 6 stiff paste soft carbon black- 3 6% H 6 10 H+ very soft carbon black". 3 4 11+ 1% 6 H-l- "The porosity numbers referred to in the above tables are merely a rough comparative index. The number 10 represents a very porous prod-- uct, whereas the number 1 represents a very slightly porous product. Intermediate degrees of porosity have been given intermediate numbers. The porosity numbers in the vertical columns are comparative, but the porosity numbers between the 140 F. cured product and the 200 F. cured product should not be directly compared as they are each upon a separate basis of comparison. The hardness abbreviations have the following significance: H=hard; H+=hard plus; S=soft; Sl=slight; V=very. It appears that processed clay, titanium dioxide and hard carbon black are among the fillers most inclined to augment the cured hardness. On the other hand, asbestos flour and calcium carbonate act as cure inhibitors.

The present applicants have found that in instances where a filler such as asbestos flour tends tofslow up or prevent a ready thorough cure, this inhibition can oftentimes be ofiset by incorporating into the composition appropriate quantitles of highly active catalysts, including materials such as benzo-trichloride, e. g. to 3 parts of a "composition comprising 100 parts of a viscous furfuracetone condensation product and 150 parts of curing agent No. 17792 there is added 0.2

part of zinc oxide, 0.2 part of benzo-trichloride and 3 parts of asbestos flour-the resultant composition reacts and sets up to a porous infusible mass on standing overnight at room temperature, or at 140 F. it sets up in 60 minutes. The same composition, but minus the asbestos, set up after '4 hours at room temperature or after 15 minutes at 140? F. i

Products of considerable commercial utility 'can be prepared in the following manner... A base stock (No. 31752) is prepared by mixing 150 parts of curing agent No. 17792 with 105 parts of composition No. 31750. Composition No. 31750 is prepared by ball milling a mixture comprising 75 parts of a liquid furfuracetone condensation product and parts of a solid furfuracetone condensation product with 5 parts of commercial zinc oxide. .The base stock is then mixed with suitable fillers as is indicated in Table IX. L

' "Products formulated as per above are conveniently cured at temperatures in the neighborhood of 140 F. For'the best results and in order to assure a minimum porosity it is recommended to cure under 'pressu'e or alternatively to age or mellow the compositions by letting them stand. for 4 or more daysatroom temperature prior to the application of higher temperatures.

Wehave thus far considered only the use of curing agents derived from the saturated ch10- rination products of furfural andthe active derivatives procurable therefrom. The applicants wish to stress, however that homologues and analogues of iurfural can also serve as the base of the curing agents. Furthermore, in addition to chlorination products one may utilize halogenation products containing the elements iodine, bromine or fluorine. 'The examples that follow clearly demonstrate these aspects.

ErampZe2a.One hundred parts of a mixture comprising solid and liquid condensation products of furfuracetone are admixed with 5 parts of zinc oxide and 20 parts of the saturated chlorin'ation product of "a-methyl furfural as curing agent. The above potentially reactive composition may readily be cured upon the application of heat. H

Example 2b.One hundred parts of a mixture comprising solid and liquid condensation productsof furfuracetone are'admixed with 5 parts of zinc oxide and 20 parts saturated chlorination product of a-ethyl furfural as curing agent. The above potentially, reactive composition may readily be curedupon the application of heat.

Example 2c.--One hundred parts of a mixture comprising solid and liquid condensation prodnets of furfuracetone are admixed with 5 parts of zinc oxide and20 parts of a curing a ent prepared by addingthe equivalent of two atoms of iodine dissolved in carbon tetrachloride to a solution of furfural in carbon tetrachloride and, aftelflreaction, passing in "chlorine until the compound is fully saturated and then isolating the same by distilling off the volatile solvents. The above potentially reactive composition may readily be cured upon the application of heat.

Example Zcar-Inthe' foregoin example the halogen element iodine was directly introduced into the heterocyclic nucleus of the five memberedring. It is also possible to introduce iodine into the complex by indirect means, e. g., the saturated chlorination product of furiural is heated with potassium iodide (in a proportion such'that the number-of iodine atoms correspond to about. one fourth the number of the chlorine atoms'in thecompound) in the presence of xylenew One maythen -mix together parts of a mixture comprising solid and liquid condensation. products oiefurfuracetone, 5 parts this;

of zinc oxide and 20 parts of the afore-described iodine containing curing agent. The above po tentially reactive composition may readily be' cured upon the application of heat.

Example .2cb .-In a somewhat analogous manner it is possible to introduce a wide variety of phide in the presence of methanol one procures a reactive sulphur containing derivative which can function as curing agent. The aforesaid sulphur-containing curing agent may be subst tuted for the curing agent of any of the forego-fi ing examples. v

Example 2d.--One hundred parts of a mixture comprising solid and liquid condensation products of fur-furacetone are admixed with 5 parts of zinc oxide and 20 parts of a curing agent prepared by adding the equivalent of two atoms of bromine dissolved in chloroform to a solution of iurfural dissolved in carbon tetrachloride and after reaction passing in chlorine until the compound has become saturated and then iso} latin the said compound by distilling off the volatiles. The above potentially reactive composition may readily be cured upon the application of heat.

Example 2e.--One hundred parts of a mixture comprising solid and liquid condensation products of furfuracetone are admixed with 5 parts of zinc oxide and 20 parts of a curing agent prepared by passing the equivalent of two atoms of fluorine (prepared electrically from hydrogen fluoride in the presence of potassium fluoride) into a solution of furfural dissolved in dichlorodifluoro-methane and then passing in chlorine until the compound has become saturated, .followed by the isolation of the compound by distilling off the volatiles. The above potentially reactive composition may readily be cured upon the application of heat.

Example 2).One hundred parts of a mixture comprising solid and liquid condensation products of furfuracetone are admixed with 5 parts parts of zinc oxide and 20 parts of the saturated chlorination product of a-thiophen aldehyde (the latter may be obtained from thienylglyoxylic acid). The above potentially reactive composition may readily be cured upon the application of heat.

Example hot-100' parts of a mixture comprising the solid and liquid condensation products of furfuracetone are admixed with '5 parts of zinc oxide and 20 .parts of the saturatedchlorination product of a-pyrrole aldehyde (the latter may be obtained through the reaction .of chloroform and potassium hydroxide upon pyrrole). The holagenation products of the pyrrole aldehydes are perhaps structurally different from those derived from the aldehydes of furane and thiophen. These differences are probably attributable to the presence of the 'imine :hydrogen in the nucleus and unusualreactivity of the .methine hydrogen. :However, for the purposes of the present invention the saturated halogenation products of the aldehydes .of pyrrole may 'be looked upon as equivalents for the saturated halogenation product of furfural inasmuch :as they, too, possess the unique functional attribute of being able to bring about the cure of various substances. The above potentially reactivecomposition may readily'be cured upon the applica- -;tion"of rheat. jrWhile .on the subject of 'turfuracetone-prod- 'the molecular weight of the same.

u'cis applicants wish to point out that the reactivity or speed of cure of the'furtura'cetone condensation products appears to be related to Thug-the thinly fluid non-resinous products are the slowest curing. On the other hand the solid resinous products cure-muclr more rapidly. The j higher the molecular. weight (which; appears to :go hand in hand'with the fusion point) the more rapid the cure- From the practical stand point it isoftentimes'dimcuIt to mix the reactive curingflagents with a solid condensation product, particularly if it. be possessed of ahigh melting point, because the temperature required to fuse the 'same is too close to the'critical temperature at which the mass will spontaneously set up and cure. For this reason it is usually desirable to utilize furfuracetone condensation products in liquid form so as to permit the more ready incorporation of the reactive curing agent (which latter are preferably in liquid form)'. It so happens that it is much easierto prepare either the non-resinous thinly liquid furfuracetone product or the solid furfuracetone product. It is advantageous to mix thinly fluid fur'furacetone condensation products with solid furfuracetone condensation products so as to procure mixtures of good working properties. In this manner it is possible to secure an added measure of control over the reactivity of the potentially reactive compositions that are produced by mixing the afore co-agents with active curing agents.

An almost endless variety of modifications may be effected by including in any of the products of the above examples other materials specifically selected to impart special attributes to the ultimate composition. Thus one may incorporate other resins of a type which mayor may not be susceptible to cure via the saturated halogenation products of the aldehydes of the mono hetero atomic five membered rings or their reactive derivatives. Similarly one may incorporate plasticizers, particularly those of the ester type, including alkyd resinous plasticizers. Plasticizers comprising chlorinated products such as chlorinated biphenyls are useful. Materials such as cashew nut shell liquid, its condensation products and its variou derivatives are extremely useful in this connection. Rubbery materials, particullarly the butadiene acrylonitrile copolymenrubbers, have been found to be extremely compatible. While fibrous cellulosic fillers and asbestos fillers are not particularly recommended, there are other fibrous materials such as glass flock and glass cloth which may advantageously be utilized to produce materials of great strength. i

It is interestin to note that the reactive curing agents utilized in thepursuitof the presentinvention are equally effective with both the nonresinous furfuracetone condensation products and the distinctly resinous solid .furfuracetone condensation products. This constitutes an exceptional instance because as :a general rule only polymeric substances readily lend themselvesfor use in the present invention.

It will be noted that the foregoing examples have been confined to the use of furfuracetone condensation products as the co-agent. We have 'sented. represents perhaps only oneipercent of the findings made by the present applicants in connection with furfuracetone condensation prod- 

5. POTENTIALLY REACTIVE CURABLE COMPOSITIONS CONSISTING OF A CURING AGENT SELECTED FROM THE CLASS CONSISTING OF THE SUBSTANTIALLY FULLY SATURATED HALOGENATION ADDITION PRODUCTS OF THE ALDEHYDES OF THE MONO HETERO ATOMIC FIVE MEMBERED RINGS AND THEIR PARTIALLY DEHALOGENATED REACTIVE DERIVATIVES, IN ADMIXTURE WITH A POLYMERIC ORGANIC COMPOUND CONTAINING WITHIN ITS STRUCTURE, ATTACHED VIA COVALENT BONDS, A PLURALITY OF FUNCTIONALLY REACTIVE ATOMIC GROUPS KNOWN TO BE REACTIVE WITH SAID CURING AGENT SAID REACTIVITY BEING DETERMINED BY BRINGING ANY COMPOUND "XY" INTO CONTACT WITH SAID CURING AGENT, WHERE "X" DENOTES A NON-REACTIVE RESIDUE AND "Y" DENOTES SUCH GROUPS TESTED AND THE PRESENCE OF "Y" BRINGING ABOUT A REACTION, SAID REACTIVE ATOMIC GROUPS BEING PRESENT IN THE POLYMERIC ORGANIC COMPOUND IN THE PROPORTION OF AT LEAST ONE SUCH GROUP PER THOUSAND ATOMS OF THE SAID POLYMERIC ORGANIC COMPOUND, SAID SUBSTANTIALLY FULLY SATURATED HALOGENATION ADDITION PRODUCTS OF THE ALDEHYES OF THE MONO HETERO ATOMIC FIVE MEMBERED RINGS PRODUCED BY THE METHOD WHICH COMPRISES THE STEPS OF DILUTING ONE OR MORE OF SAID ALDEHYDES WITH A SOLVENT IN PROPORTION OF AT LEAST ONE MOLE OF SAID SOLVENT TO EACH MOLE OF SAID ALDEHYDE, AND THEN RAPIDLY INTRODUCING HALOGEN INTO THE SOLUTION WHILE MAINTAINING THE TEMPERATURE THEREOF BELOW THE POINT OF SPONTANEOUS DECOMPOSITION UNTIL THE ALDEHYDE HAS TAKEN UP SUBSTANTIALLY FOUR ATOMS OF HALOGEN PER MOLECULE OF ALDEHYDE AND THE POINT OF SUBSTANTIAL SATURATION HAS BEEN REACHED, AND THE SAID PARTIALLY DEHALOGENATED REACTIVE DERIVATIVES PRODUCED BY THE METHOD WHICH COMPRISES DEHALOGENATING THE SAID FULLY SATURATED HALOGENATED ADDITION PRODUCTS TO A POINT WHERE THE AVERAGE HALOGEN CONTENT OF THE RESULTANT PARTIAL DEHALOGENATION PRODUCT IS EQUAL TO NOT LESS THAN ONE ATOM OF HALOGEN PER MOLECULE OF ALDEHYDE THAT ENTERED INTO THE MAKING OF SAID SATURATION HALOGENATION ADDITION PRODUCTS. 